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Microwave-Assisted Preparation of Inorganic Nanostructures in

Liquid Phase
Ying-Jie Zhu* and Feng Chen
State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy
of Sciences, Shanghai 200050, People’s Republic of China
4.4. Metal Chalcogenides 6509
4.5. Other Nanostructured Materials 6509
5. Microwave-Assisted Preparation of Nanostruc-
tures in Other Solvents 6511
6. Microwave-Assisted Preparation of Nanostruc-
tures in Mixed Solvents 6515
6.1. Binary Solvent Systems 6515
6.1.1. Water/Polyols 6515
6.1.2. Water/Alcohols 6519
6.1.3. Water/N,N-Dimethylformamide 6521
6.1.4. Water/1,2-Ethylenediamine 6521
6.1.5. Other Binary Solvents 6521
6.2. Ternary and Multinary Solvent Systems 6524
CONTENTS 7. Microwave-Assisted Self-Assembly of Nanostruc-
tures 6525
1. Introduction 6462 8. Comparison of Microwave Heating with Conven-
1.1. Microwave Chemistry and Microwave Ef- tional Heating 6529
fects 6464 9. Future Prospects and Challenges 6539
1.2. Rate Accelerations by Microwave Heating 6466 Author Information 6540
1.3. Microwave-Assisted Preparation in Different Corresponding Author 6540
Solvents 6469 Notes 6540
1.4. Microwave-Assisted Preparation in an Open Biographies 6540
Reaction System 6470 Acknowledgments 6540
1.5. Microwave-Assisted Preparation in a Closed Abbreviations 6540
Reaction System − Microwave-Assisted References 6541
Hydrothermal/Solvothermal Method 6470
2. Microwave-Assisted Preparation of Nanostruc-
tures in Aqueous Solution 6471
2.1. Metals, Semimetals, Nonmetals, and Alloys 6471 1. INTRODUCTION
2.2. Metal Oxides 6477 The heating effect of microwaves was accidentally discovered in
2.3. Metal Sulfides 6483 1945 by Percy LeBaron Spencer, an American engineer and
2.4. Metal Selenides 6484 inventor, at the Raytheon Co. While working on radar
2.5. Metal Tellurides 6485 applications of microwaves, he found that a chocolate bar
2.6. Inorganic Biomaterials − Hydroxyapatite melted in his pocket. Microwaves are the electromagnetic waves
and Calcium Phosphates 6485 with frequencies ranging from 0.3 to 300 GHz and with
2.7. Other Compounds 6488 wavelengths of between 1 mm and 1 m, which are between
2.8. Inorganic/Inorganic Nanocomposites 6490 infrared and radio frequency waves in the electromagnetic
2.9. Inorganic/Organic Nanocomposites 6494 spectrum. Microwave radar equipment uses lower wavelengths
3. Microwave-Assisted Preparation of Nanostruc- of 0.01−0.25 m of the microwave band, and much of the
tures in Polyols 6495 microwave band is used for telecommunications. To avoid the
3.1. Metals, Semimetals, Nonmetals, and Alloys 6496 interference with these uses, the wavelengths used by industrial
3.2. Metal Oxides 6499 and domestic microwave apparatuses are regulated at both
3.3. Metal Chalcogenides 6500 national and international levels. The commonly used
3.4. Other Compounds 6502 frequency in laboratories and homes for microwave heating is
3.5. Nanocomposites 6503 2.45 GHz (with a wavelength of about 12.24 cm).
4. Microwave-Assisted Preparation of Nanostruc- Time is invaluable; this is also true for science, especially in
tures Using Ionic Liquids 6506 the field of synthetic chemistry where many time-consuming
4.1. Ionic Liquids and Microwave Heating Effects 6506
4.2. Metals, Semimetals, Nonmetals, and Alloys 6507 Received: July 10, 2013
4.3. Metal Oxides 6508 Published: June 4, 2014

© 2014 American Chemical Society 6462 dx.doi.org/10.1021/cr400366s | Chem. Rev. 2014, 114, 6462−6555
Chemical Reviews
trial-and-error experiments are needed. Rapid synthetic
techniques will be extremely beneficial for scientists to perform
more experiments within the same period of time to expand
their scientific creativity. Hayes even used the figurative
expression “microwave synthesis: chemistry at the speed of
light”.1 Hayes also pointed out: “Microwave synthesis is a
breakthrough technology for chemistry: an idea whose time has
come. Its use has become more widespread, and as the
technology continues to rapidly evolve, microwave synthesis
will have a dramatic impact on the world of chemistry.”1
Microwave chemistry definitively fulfills the promise of being a
fast synthetic technique.2
In today’s world, researchers in both academia and industry
are constantly challenged to consider more environmentally
benign methods for the fabrication of the desired products.
Among the 12 principles of green chemistry, the desire for
utilizing “safer solvents” and to “design for energy efficiency”
are two key principles of relevance to synthetic chemists.3 The
microwave energy is more efficient in selective heating in many
processes, which is understood to be more environmentally
friendly, requiring less energy than the conventional heating
processes.4 The American Chemical Society monograph on
Green Chemistry5 recommends that we “use methods that
minimize the energy required for a reaction to take place. For
example...catalysts or microwave radiation...” Patete et al.6
published a review article entitled “Viable Methodologies for
the Synthesis of High-Quality Nanostructures”, and they listed
the microwave-assisted synthesis as one of the environmentally
friendly methods. Dahl et al.7 published a review article entitled
“Toward Greener Nanosynthesis”, and they suggested that the
microwave synthesis is a relatively new chemical method to
facilitate reactions and could be another avenue for green
synthesis of nanomaterials. Several attributes of microwave
heating contribute to greener syntheses, including shorter
reaction time, lower energy consumption, and higher product
yield. The microwave-assisted technology can be combined
with other green chemistry strategies to make it more appealing
to green synthesis. For example, ionic liquids, solvent-free
reactions, and nontoxic precursors can be easily utilized in
conjunction with microwave heating.
The pioneering work on the microwave-assisted synthesis
was carried out in the middle of the 1980s. The research work
of Komarneni and Roy8 in 1985 was the beginning of
microwave-assisted inorganic synthesis in liquid phase, while
Gedye et al.9 and Giguere et al.10 first reported the use of
microwaves for the organic synthesis in 1986. In their
pioneering work,8 Komarneni and Roy reported the micro-
wave-assisted synthesis of titania gel spheres by the dispersal of
the polymerized titanium ethoxide solution into a two-phase
liquid suspension in kerosene followed by heating in a
microwave oven. Since these reports on the microwave-assisted
synthesis, the microwave heating technology has been receiving
increasing attention as a promising heating method.11 The
microwave heating technology is emerging as an alternative
popular heat source for rapid chemical reactions and materials
synthesis in minutes, instead of hours or even days usually
required by the conventional heating methods. Over the past
two decades, the microwave chemistry has rapidly developed
from a laboratory curiosity to a well-established synthetic
technique used in many academic and industrial laboratories
around the world. This technology will open new synthetic
pathways and allow the use of more environmentally friendly
solvents, and it will also yield cleaner products that will not
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require as much purification.12 The microwave-assisted
preparation of inorganic nanostructured materials in liquid
phase is currently a fast-growing area of research. It is expected
that the related research activities will continue to grow rapidly
in the coming years. Although most research on microwave-
assisted synthesis is still performed on a laboratory (milliliter)
scale, it is expected that this novel technology will soon be used
on a larger, perhaps even production, scale.13
Nowadays, more laboratories of materials science as well as
organic and pharmaceutical chemical laboratories have been
equipped with microwave reactors. Many early publications on
microwave-assisted synthesis were carried out in household
microwave ovens, and experimental parameters like microwave
power, reaction temperature, and pressure inside the vessel
were not precisely known in household microwave ovens.
These uncertainties led to poor control over the synthesis and a
lack of reproducibility of experiments. Therefore, the use of
commercially available specially designed microwave reactors
with built-in magnetic stirrers, and direct temperature and
pressure monitoring by various probes and sensors is strongly
recommended. It is possible to combine microwave chemistry
with the well-established liquid-phase synthesis techniques, and
the possible combinations open unique and exciting oppor-
tunities for the preparation of inorganic nanostructures in liquid
phase.2
In recent years, some review articles have been published on
the microwave-assisted synthesis of nanostructured materials,
such as metal nanostructures,13,14 nanostructured carbon
materials,15 nanoporous nanomaterials,4,16 colloidal nanocryst-
als,17 inorganic nanomaterials,2 metal oxide nanoparticles
supported on carbon nanotubes,18 and polymer nanocompo-
sites.19 Currently, timely and comprehensive review articles on
microwave-assisted preparation of inorganic nanostructured
materials in liquid phase are of great importance and
significance for the future rapid development of the related
research field.
In this Review, we do not give an exhaustive coverage of the
microwave-assisted synthesis of inorganic nanostructures in
liquid phase, but mainly cover the significant research progress
in the past decade. Many inorganic nanostructured materials
including metals, semimetals, alloys, metal oxides, metal
sulfides, metal selenides, metal tellurides, calcium-based salts
and other oxysalts, inorganic/inorganic nanocomposites, and
inorganic/organic nanocomposites, prepared by microwave
heating in various solvents including water, polyols, ionic
liquids, and mixed solvents, are classified and reviewed. The
microwave-assisted self-assembly of inorganic nanostructures in
liquid phase is discussed. In addition, the differences between
microwave heating and conventional heating in the formation
of inorganic nanostructures in liquid phase are compared.
Finally, future prospects and challenges for microwave-assisted
preparation of inorganic nanostructures in liquid phase are
discussed. For the microwave-assisted synthesis of metallic
nanostructures, we will focus on the progress made from 2005
upward, covering the new results that are not included in a
previous review.14 For the microwave-assisted synthesis of
nanostructured metal compounds, we will focus on metal
oxides and metal chalcogenides for the reasons that they are
very important functional materials both for the fundamental
research and for practical applications and that there have been
a large number of publications in the literature. However, fewer
papers have been published on the microwave-assisted
synthesis of other metal compounds such as metal halides
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Chemical Reviews
Figure 1. Temperature profile after 1 min as affected by microwave irradiation (left) as compared to treatment in an oil bath (right). Microwave
irradiation raises the temperature of the whole reaction volume simultaneously, whereas in the oil heated tube, the reaction mixture in contact with
the vessel wall is heated first. Temperature scale is in kelvin. “0” on the vertical scale indicates the position of the meniscus. Reproduced with
permission from ref 28. Copyright 2003 Kluwer Academic Publishers.
and metal nitrides; thus, less coverage will be put on these
nanostructured materials. The microwave-assisted synthesis of
zeolite membranes and metal−organic frameworks has been
reviewed by Li et al.20 and Klinowski et al.,21 respectively, and
these will not be included. In addition, the microwave-plasma
synthesis, microwave sintering, microwave processing,22 and
microwave-assisted functionalization of materials23 are not the
topics in this Review.
1.1. Microwave Chemistry and Microwave Effects
Microwave chemistry is the science of applying microwave
irradiation to chemical reactions. The basic principles of
microwave chemistry have been discussed in some review
papers.14,17,24−27 Nüchter et al.24 discussed a critical overview
of the microwave technology and focused mostly on the
reaction engineering in the microwave field. Gabriel et al.25
provided a thorough explanation of the underlying theory of
the microwave dielectric heating. The microwave heating
involves two main mechanisms, dipolar polarization and ionic
conduction. Microwaves generally heat any material containing
mobile electric charges such as polar molecules or conducting
ions in a solvent or in a solid. During the microwave heating,
polar molecules such as water molecules try to orientate with
the rapidly changing alternating electric field; thus heat is
generated by the rotation, friction, and collision of molecules
(dipolar polarization mechanism). In the case of ions, any ions
present in solution will move through the solution based on the
orientation of the electric field, and because this is in constant
fluctuation, the ion is moving in constantly changing directions
through the solution, causing a local temperature rise due to
friction and collision.12 Semiconducting and conducting
samples heat when ions or electrons within them form an
electric current and energy is lost due to the electrical resistance
of the material (ionic conduction mechanism).
The microwave heating technology is emerging as an
alternative heat source for rapid volumetric heating with
shorter reaction time and higher reaction rate, selectivity, and
yield as compared to the conventional heating methods. As a
result, microwave heating has opened the possibility of realizing
fast chemical reactions and rapid materials preparation in very
short time periods, usually in minutes, instead of hours or even
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days usually required by the conventional heating methods,
leading to relatively low cost, energy saving, and high efficiency
for materials production.
In contrast, the conventional heating usually involves the use
of an electric furnace or oil bath, which heats the walls of the
reactor and then the reactants by convection or conduction.
The reactor acts as the intermediary to transfer thermal energy
from the external heat source to the solvent, and ultimately to
the reactants. The core of the sample takes much longer to
achieve the target temperature. Such a pathway typically leads
to thermal gradients throughout the bulk media, and to
inefficient and nonuniform reactions, which may cause serious
issues in the scale-up production. In contrast, the microwave
heating is able to heat target materials without heating the
entire furnace or oil bath, which saves time and energy. Figure 1
shows the comparison of temperature profiles by microwave
heating and oil bath.28
The energies of microwaves are not high enough to break
typical chemical bonds. For example, the energy of a microwave
photon at a frequency of 2.45 GHz is only 1.0 × 10−5 eV, and
the energies at 0.3 and 30 GHz are 1.2 × 10−6 and 1.2 × 10−3
eV, respectively.24 These energies are too low to cleave
chemical bonds, even lower than the Brownian motion, and can
only affect molecular rotations.29 Thus, microwave chemistry is
based on efficient heating of materials, not inducing chemical
reactions by direct absorption of electromagnetic radiation, as
applied in photochemistry processes.2 Jhung et al.30 reported
that microwave irradiation accelerated not only nucleation but
also crystal growth.
The ability of microwave heating for a specific material or
solvent at a given frequency and temperature is determined by
the so-called loss tangent tan δ = δ′′/δ′, where δ′′ is the
dielectric loss, representing the conversion efficiency of the
electromagnetic radiation into heat, and δ′ is the dielectric
constant, describing the polarizability of molecules in the
electric field.17,25,26 The loss tangent value depends on the
temperature and frequency, and these two parameters strongly
affect the penetration depth, which is defined as the point
where 37% of the initially irradiated microwave power is still
present.24
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Chemical Reviews
The microwave penetration depth is inversely proportional
to the loss tangent. The solvents and materials with high loss
tangents have short penetration depths. In the case of water,
which is the most frequently used solvent, the penetration
depth at room temperature is just a few centimeters, and this
has far-ranging implications for the scale-up of microwave
synthesis. For pure water and most of the organic solvents, the
loss tangent decreases with temperature; that is, the absorption
of microwave irradiation decreases with temperature, which
means that microwave heating at high temperatures may
become somewhat difficult.2 Horikoshi et al.31 reported that the
dielectric loss factors decreased (∼72% for a microwave
frequency of 2.45 GHz and ∼60% for 5.8 GHz) with increasing
temperature of water from 22 to 99 °C. The penetration depth
of the 2.45 GHz microwaves in water increased 2.7-fold from
∼1.8 to 4.8 cm when the temperature increased from 22 to 99
°C, whereas the penetration was rather shallow for the 5.8 GHz
microwaves (from 0.34 to 0.62 cm, i.e., a 1.8-fold increase), as
shown in Figure 2. The penetration depth is proportional to the
Figure 2. Temperature profiles of the changes in dielectric loss factor
(δ″) and penetration depth (cm) of 2.45 and 5.8 GHz microwaves in
water. Reproduced with permission from ref 31. Copyright 2009
Elsevier B.V.
wavelength of applied microwaves. For example, the
penetration depths in water are ∼1.8 and 0.34 cm at 22 °C
for the 2.45 and 5.8 GHz microwaves, respectively,31 and the
penetration depths in oleylamine are 22.8 and 3.8 cm for 2.45
and 5.8 GHz microwaves, respectively.32 The gap shown in
Figure 2 for dielectric loss factors of the 2.45 and 5.8 GHz
microwave frequencies in water is proportional to the difference
in frequency. For low loss dielectric (i.e., δ′′/δ′ much smaller
than 1), the depth (Dp, in cm) to which the microwave
radiation penetrates the microwave absorbing media can be
estimated from eq 1,33 where λ0 is the wavelength of the
radiation (λ0(2.45 GHz) = 0.122 m and λ0(5.8 GHz) = 0.0517 m). Dp
denotes the depth at which the power density of microwaves is
reduced to 1/e of its initial value.
⎛ λ ⎞⎛ ε′ ⎞
D P = ⎜ 0 ⎟⎜ ⎟ to 1 s) microwaves. The dependence of properties of BaTiO3
⎝ 2π ⎠⎝ ε″ ⎠
32
Horikoshi et al. investigated the effect of microwave
frequency (5.8 and 2.45 GHz) on the formation of Au
nanoparticles in ethylene glycol (EG) and oleylamine. Oleyl-
amine has a low dielectric constant and is not dielectrically
heated by 2.45 GHz microwaves. They found that a change in
microwave frequency from 2.45 to 5.8 GHz at equal microwave
power levels led to the formation of Au nanoparticles in the
nonpolar solvent of oleylamine; however, a change in the
Review
microwave frequency had almost no effect on the size and
shape of Au nanoparticles obtained in the polar solvent of EG
at identical microwave power levels. It is usually assumed that
the microwave-assisted synthesis does not occur in nonpolar
solvents because they are not microwave absorbers. However,
this study has shown that it is possible to form Au nanoparticles
even in a nonpolar solvent at the same microwave power and
solution composition using microwaves with a higher frequency
(e.g., 5.8 GHz). In contrast, in a polar solvent such as EG, the
size and shape of Au nanoparticles showed little frequency-
dependent effect.
There is a significant difference between the variable-
frequency and fixed-frequency microwave heating. Microwaves
can penetrate a solvent with different depths by varying
frequencies (wavelengths). During a variable-frequency micro-
wave heating process, a selected bandwidth is swept around a
central frequency in a specified time, which keeps the
microwave energy from remaining focused at any given
location for more than a fraction of a second. In the presence
of standing waves of electric fields during constant frequency
microwave heating, the arcing occurs from a charge buildup in
conductive materials. Arcing problems and localized heating
can be eliminated using the variable-frequency microwave
heating.34 Jiang et al.35 prepared Ag nanoparticles with a narrow
size distribution and with a high yield by the variable-frequency
microwave heating. The Suib group reported microwave-
assisted two-step hydrothermal synthesis of cryptomelane-type
manganese oxides (OMS-2) at different microwave frequencies
and also using the variable-frequency heating. They found that
OMS-2 prepared at a high-frequency limit of 5.5 GHz showed
the highest conversion (50%) for the oxidation of 2-
thiophenemethanol to 2-thiophenecarboxaldehyde among all
of the tested OMS-2 samples.34 The Suib group also
investigated the effect of microwave frequency on the
microwave-hydrothermal product of nanocrystalline tetragonal
BaTiO3 with particle sizes ranging from 30 to 100 nm.36 They
systematically investigated the effects of microwave frequency,
microwave bandwidth sweep time, and aging time on the
microstructure, particle size, phase purity, surface area, and
porosity of the as-prepared BaTiO3 nanostructures. They found
that the particle size, morphology, and surface area of the
products were influenced by the microwave frequency and
bandwidth sweep time. High microwave frequency (5.5 GHz)
and variable frequency (3−5.5 GHz to 1 s) led to spherical
BaTiO3 nanoparticles with a narrow and unimodal particle size
distribution. However, the products prepared via the conven-
tional heating under similar conditions exhibited bimodal
particle size distributions with irregular grain sizes. BaTiO3
prepared using the standard 2.45 GHz microwaves yielded
nanoparticles with a cubic structure. The surface areas of the
prepared powders decreased with the processing time using 4.0
and 5.5 GHz microwaves, but increased gradually with
extended processing time in variable frequency (3−5.5 GHz
(1)
on microwave frequency may be due to different transverse
magnetic modes at different frequencies.36
The effect of microwave power on the formation of
nanostructured materials has also been investigated. Seol et
al.37 investigated the effect of applied microwave power on the
formation of Au nanoparticles using HAuCl4 and sodium citrate
as reactants in aqueous solution. Using a high microwave power
to increase the temperature ramping rate led to homogeneous
nucleation, smaller average size, and narrower size distribution
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Chemical Reviews
of Au nanoparticles. Yang et al.38 investigated the effect of
microwave power on the morphology of Ag nanostructures.
The results showed that a medium microwave power of ∼320
W × 3−4 min produced Ag nanowires of 6−8 μm in length,
while Ag nanowires were shortened to 2−4 μm at a lower
power. At a higher microwave power, Ag particles dominated
the product with short nanowires of ∼3−4 μm. In addition, the
combination of 800 W × 0.5 min + 320 W × 2.5 min resulted
in mainly uniform Ag nanowires up to 10 μm in length with a
small quantity of Ag particles. However, prolonged treatment at
800 W during the first heating stage and the reversed
combination of 320 W + 800 W led to a high yield of Ag
particles.
The microwave heating has two types: pulsed microwave
heating and continuous microwave heating. Shen et al.39
investigated the difference between the pulsed microwave
heating and continuous microwave heating in the synthesis of
WC nanoparticles using (NH4)6H2W12O40·xH2O in mixed
solvents of 2-propanol and water. The pulsed microwave
heating produced WC nanoparticles with an average particle
size of 21.4 nm with a 15 s-on and 15 s-off heating mode for 20
times; however, the particle size increased to 35.7 nm by the
continuous microwave heating for 5 min.
Gedye et al.40,41 reported the effects of several factors, such
as sample volume, solvent, homogeneous and heterogeneous
reactions, size of reaction vessel, and power level, on the rate
enhancements in microwave-assisted organic synthesis. Bonac-
corsi and Proverbio42 investigated the microwave synthesis of
NaA zeolite using two reaction flasks with sizes of 100 and 500
mL. If the penetration depth is much less than the thickness of
the bulk material, only the external part is dielectrically heated,
while the remaining part is heated by convection. The reaction
mixture (50 g) was treated in two spherical glass reactors. In
such a way, the same amount of reaction mixture had different
surface to volume ratios exposed to microwaves. The product
with a lower crystallization and higher level of impurities was
obtained in the reactor with a volume of 500 mL, indicating an
excess of energy transferred to the mixture. Conner et al.43
investigated the synthesis of silicalite in either an 11 mm
diameter microwave reactor or a 33 mm diameter microwave
reactor. They found from simulation that the distributions of
microwave energies within the reactors were different, and the
morphology and yield of the resultant zeolite also differed.
Larger uniform silicalite crystals were obtained in the larger
reactor in which the variation in microwave energy distribution
was greater.
Panzarella et al.44 investigated several microwave synthesis
parameters such as the reaction vessel size, precursor volume,
microwave power delivery, and microwave cavity design. The
syntheses of NaY zeolite and β-zeolite were carried out under a
number of different conditions to determine the influence of
these parameters on the nucleation rate, crystallization rate,
particle size, and morphology. They found that the nucleation
and crystallization rates of NaY and β-zeolite were more rapid
in the multimode CEM MARS-5 oven as compared to the
single-mode CEM Discover oven. The higher synthesis rate in
the MARS-5 oven may result from the multimode microwave
electric field distribution. Lower formation rates of NaY and β-
zeolite observed in the Discover oven with a circular waveguide
may be the result of a more uniform microwave electric field
distribution. Changes in the reaction vessel size and precursor
volume were found to influence the formation rate of zeolite.
They also reported that the microwave reactor engineering
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could lead to different variations in spatial or temporal
variations in microwave exposure, and different extents of rate
enhancement. The reactor geometry significantly influenced the
reaction rate. The larger diameter reactor (33 mm) yielded a
faster crystallization for the synthesis of zeolites in the MARS-5
microwave oven. They suggested that future studies of
microwave rate enhancements must specify the reactor
engineering parameters for the experiments.44
The in situ stirring in the reaction system plays an important
role in the microwave-assisted synthesis of inorganic nano-
structures.45,46 The stirring is important for achieving uniform
microwave irradiation of the reaction system especially in a
large vessel. Komarneni et al.45 reported that stirring under
microwave-hydrothermal conditions in the temperature range
of 150−200 °C led to enhanced yields as well as smaller and
more uniform BaTiO3 nanoparticles as compared to those
obtained in the static environment under otherwise similar
conditions. Well-dispersed BaTiO3 nanoparticles with smaller
sizes of ∼30 nm were synthesized at 180 °C under stirring,
while aggregated and larger particles with sizes of 60−100 nm
were obtained without stirring. Katsuki et al.46 prepared cubic
BaTiO3 nanoparticles using commercial TiO2 and Ba(OH)2 in
distilled water at 90 °C by a home-built single-mode
semicontinuous microwave reactor. The conversion ratio of
TiO2 to BaTiO3 was 97.6% and 100% for 5 and 15 min under
stirring, respectively. In comparison, the conversion ratio was
only 62−65% at 90 °C for 15 min without stirring.
1.2. Rate Accelerations by Microwave Heating
Many experiments have shown that the microwave heating can
significantly increase the rates of chemical reactions by several
orders of magnitude. Chemical reactions that otherwise take
hours or even days to complete by using the conventional
heating methods can be completed in very short periods of time
(minutes) under microwave irradiation. Even chemical
reactions that do not occur under the conventional heating
conditions can be performed under similar conditions by the
microwave heating. These experimental results cannot be well
explained by the effect of rapid microwave heating alone,
leading to the interpretation of the existence of the “specific
microwave effects” or “nonthermal microwave effects”.
The synthesis of materials involves the processes of
nucleation and crystal growth. The question arises as to
which stage is selectively accelerated under microwave
irradiation. Jhung et al.30 synthesized microporous materials
of silicalite-1 and VSB-5 molecular sieves by the conventional
electric heating and microwave irradiation to estimate the
relative accelerations at the stages of nucleation and crystal
growth. They found that microwave irradiation accelerated not
only nucleation but also crystal growth. However, the effect of
microwave irradiation appeared to be much more significant on
nucleation relative to crystal growth. Because of the
accelerations in both stages, the overall synthesis times for
silicalite-1 and VSB-5 decreased by ∼30- and 12-fold,
respectively, by using microwave heating. The microwave
nucleated precursors had higher population of nuclei with
smaller sizes than the precursors nucleated by the conventional
heating.
The studies on the mechanisms of microwave heating are
even complicated by the fact that the rate enhancements of
chemical reactions are dependent on many complex factors.
Gedye et al.40,41 reported the effects of several factors, such as
sample volume, solvent, homogeneous and heterogeneous
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Chemical Reviews
reactions, size of reaction vessel, and power level, on rate
enhancements in microwave-assisted organic synthesis. The
rate enhancements of between 5 and 1240 were found for
several classes of organic reactions. They proposed that the rate
enhancements were caused predominantly by the rapid
superheating of the solvent by microwaves. They also found
that the presence of ions in the reaction mixture increased the
microwave heating rate. When ions were present in solution,
the maximum heating rate was observed at the smallest volume.
Scaling up the chemical reaction led to a slightly lower reaction
rate and a lower yield of the product for the same reaction time.
Although the reaction rate was reduced when the reaction was
scaled up, large rate enhancement was still observed. Robinson
et al.47 investigated the experimental phenomena in the single-
mode microwave reactor. They highlighted several situations
where experimental observations were often misinterpreted as
“specific microwave effects”. The simulations and heating
experiments were used to investigate the quantitative effects of
the solvent type and volume, vessel materials and internals, and
stirring rate on the distribution of the electric field, power
density, and heating rate. They found that significant
concentrations of the electric field and power density existed
around the edges of stirrers, internal temperature probes, and
other protruding objects, which could cause large thermal
gradients and local heating. The volume of solvent and vessel
material had a significant impact upon the electric field
distribution. The temperature recorded during microwave
heating experiments depended upon both the measurement
method and the position of the measuring device within the
system.
The current debate on rate accelerations by microwave
heating focuses on whether there are the “specific microwave
effects” or “nonthermal microwave effects”.17,20,29,48−54 Bagh-
banzadeh et al.17 gave a thoughtful discussion about the
nonthermal effects of microwave heating. They have proposed
that, in addition to the thermal/kinetic effects, microwave
effects that are caused by the uniqueness of the microwave
dielectric heating mechanisms must also be considered. These
effects should be termed as “specific microwave effects”, which
are defined as “rate accelerations that cannot be achieved or
duplicated by the conventional heating, but are essentially still
thermal effects”. However, the “nonthermal microwave effects”
should be classified as rate accelerations that can be rationalized
by neither purely thermal/kinetic nor specific microwave
effects. They proposed that nonthermal effects are supposed
to result from direct interaction of microwaves with specific
molecules or materials in the reaction medium, which is not
related to a macroscopic temperature effect.
Examples of “specific microwave effects” include the
superheating effect, selective heating of polar species in a
microwave transparent (or at least less absorbing) medium,
formation of “molecular radiators” by direct coupling of
microwave energy to specific reagents in homogeneous
solution, and elimination of vessel wall effects caused by
inverted temperature gradients.2 Microwave heated liquids may
have boiling points of 10−20 °C higher than the conventional
boiling point at the atmospheric pressure, and this superheating
effect makes the comparison of the reaction rates under the
conventional heating and microwave heating rather difficult.
However, superheating can be strongly suppressed by stirring.2
“Hot spots” are a thermal effect that arises as a consequence of
the inhomogeneity of the applied microwave field and selective
heating. In a heterogeneous reaction system composed of
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different reactants, the microwave selective heating of different
components of the system may occur, leading to inhomoge-
neous energy dissipation and temperature gradients. The heat
transfer processes take place from zones with a higher
temperature (hot spots) to those with a lower temperature. If
the heat conduction rate is high between zones, hot spots
disappear as the components rapidly reach the thermal
equilibrium. In a system where the heat transfer is slow, the
presence of steady-state hot spots may exist and enhance the
rate of the chemical reaction within that hot zone. The size of
hot spots was estimated to be as large as 100 μm.52 Washington
and Strouse55 investigated the growth of CdSe and CdTe
nanocrystals by selective heating of the chalcogenide precursor
in microwave nonabsorbing alkane solvents. The chalcogenide
precursor selectively absorbed the microwave energy, resulting
in the instantaneous nucleation and growth upon microwave
irradiation.
Two models of the mechanism have been proposed for
microwave-induced reaction rate enhancements.49 The first
proposed mechanism assumes that, although the reaction time
is drastically reduced for a microwave-induced reaction, the
kinetics or mechanism of the chemical reaction is not altered;
that is, the reaction rate enhancement is simply due to the
thermal heating effect. The rapid heating rate and super-
heating/“hot spots” of the reaction system under microwave
irradiation result in a dramatically increased reaction rate.
Another proposal assumes that there are “nonthermal micro-
wave effects” in addition to the thermal effects discussed above.
It was proposed that the effects of microwave irradiation in
chemical reactions are a combination of the thermal effects and
nonthermal effects.52 Nonthermal effects result from direct
interaction of microwaves with specific molecules or materials
in the reaction medium. In this regard, the microwave heating
strongly interferes with possible nonthermal effects, and these
are difficult to separate in the mechanism studies.52 The
reported “nonthermal microwave effects” include varied
activation energy, increased collision efficiency by mutual
orientation of polar molecules, and possible excitement of
rotational or vibrational transitions.27,50,52 Perreux and Loupy50
proposed a rationalization of microwave effects in organic
synthesis based on medium effects and mechanistic consid-
erations. They proposed that under microwave irradiation the
pre-exponential factor A in the Arrhenius law k = A exp(−ΔG/
RT), which is representative of the probability of molecular
impacts, increases. The collision efficiency can be effectively
influenced by mutual orientation of polar molecules involved in
the reaction. Godinho et al.53 prepared Gd-doped CeO2
nanorods by the microwave-assisted method; they postulated
that the growth process under microwave irradiation increased
the effective collision rate due to the increase in the collision
cross-section of the particle. However, the effect of microwave
heating on the activation energy of chemical reactions has been
under debate, and some conflicting results have been reported,
and this topic will be discussed in section 8.
Jacob et al.49 published a review article to discuss thermal and
nonthermal interactions of microwaves with materials. They
discussed some comparative examples of organic reactions
performed both by the microwave heating and by the
conventional heating, and concluded that the rate enhance-
ments under microwave irradiation were purely due to thermal
reasons. They classified reaction rate enhancements into the
following categories: (1) The first is reaction rate enhancement
due to “hot spots”/localized heating effect. The acceleration of
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Chemical Reviews
the chemical reaction by microwave heating was suggested to
be due to either of the following reasons: superheating effect
due to the presence of a large number of ions, superheating
effect at the boundary between nonmiscible liquids along with
efficient mixing of reactants, and rapid temperature ramping of
the reaction system caused by microwave dielectric heating. (2)
The second is reaction rate enhancement due to molecular
agitation. Microwaves cause rapid shift of the dipoles in the
molecules. The intermolecular bonds hinder the rotation of the
dipoles, causing a lag in the dipoles following the electro-
magnetic radiation. This process may also be viewed as
molecular agitation or stirring, which may account for the
nonthermal effects of microwaves. (3) Third is reaction rate
enhancement due to improved transport properties of
molecules. The slowest step in solid-state reactions is the
diffusion of reactants. Because the rate of a reaction is
controlled by the slowest step, any process that can enhance
the diffusion of reactants will lead to a significant rate
enhancement. Microwave irradiation can enhance the diffusion
of reactants as compared to the conventional heating at the
same temperature. (4) The final category is reaction rate
enhancement due to other reasons.
Kuhnert51 discussed whether there are “nonthermal micro-
wave effects” in organic synthesis. Two representative examples
of microwave chemistry were provided to illustrate the
confusion caused by an uncritical consideration of published
results. Both examples showed the differences between the
reaction conditions of the conventional thermal and microwave
heating methods, and demonstrated the difficulties in such a
comparison. They cautiously concluded that all speculation of
special and nonthermal effects in microwave heating has no
basis. Kappe29 and Baghbanzadeh et al.17 proposed that in most
cases the observed rate enhancements under microwave
irradiation are simply a thermal/kinetic effect, resulting from
high reaction temperatures that can be rapidly attained by
microwave heating. Naturally, such temperature profiles of
microwave heating are very difficult if not impossible to
reproduce by the conventional thermal heating. Therefore, the
comparisons of the microwave heating processes with the
conventional heating ones under exactly the same conditions
are inherently challengeable. Baghbanzadeh et al.17 emphasized
that practical difficulties in accurate measurement of reaction
temperature during microwave heating often contribute to
misinterpretations of the experimental results. Langa et al.48
also ascribed the temperature measurement of the reaction
system as one reason for the controversies over the
“nonthermal microwave effects”. However, the effect of the
microwave frequency on the nanocrystal formation at the
constant temperature would be a genuine indication of the
involvement of the nonthermal microwave effects.17 Baghban-
zadeh et al.17 pointed out that extreme care must be taken in
the interpretation of published data. The readers must be aware
that it is probable that in the next few years the majority of
claimed “specific microwave effects” and “nonthermal micro-
wave effects” involved in the nanocrystal synthesis will have to
be reinterpreted as the result of erroneous temperature
measurements.
To tackle this problem, the Kappe group has done inspiring
work on the comparisons between microwave heating and
conventional heating, as they designed smart experiments to
discriminate the thermal and nomthermal effects.54 They used
the reaction vessel made from silicon carbide (SiC) and a
single-mode microwave reactor that allows simultaneous
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temperature monitoring by the external infrared and internal
fiber optic probes. SiC is a strongly microwave-absorbing and
chemically inert ceramic material with a very low thermal
expansion coefficient that can be used at extremely high
temperatures (melting point ∼2700 °C). Microwave irradiation
induces a flow of electrons in the semiconducting SiC that
heats the reaction vessel very efficiently through the resistance
heating mechanism. They proposed that because of the high
microwave absorptivity of SiC, any material contained within
the SiC vial will be effectively shielded from the electro-
magnetic field. For this purpose, custom-made 10 mL reaction
vials made from sintered SiC and standard microwave-
transparent Pyrex vials with the exact same geometry were
used. Their experiments provided a good method to heat a
reaction system by the conventional heat transfer mechanism
and not by dielectric heating effects, although using microwave
irradiation. Eighteen previously published microwave-assisted
organic chemical reactions were investigated in comparison
with the conventional heating; however, they did not find any
significant differences in terms of the conversion, purity, and
product yield between experiments performed in SiC vials and
microwave-transparent Pyrex vials. They proposed that only
bulk temperature effects were responsible for the observed rate
enhancements and that the electromagnetic field had no direct
influence on the reaction pathway.
Conner and Tompsett56 proposed that microwaves can
change the energies and/or “effective temperature” of
individual species at interfaces. Species sorbed or formed on
a surface are more susceptible to microwave interactions. The
sorbed species with different permittivities exhibit different
effective temperatures. Microwave exposure can change the
relative energies of the intermediate species in a given
sequence, which will influence the overall kinetics. The overall
reaction rate for a sequence of metastable intermediates in a
reaction can be increased significantly even if the activation
energy maxima do not decrease. They simulated the kinetic
consequences for a series of reactions due to changes in the
effective temperature of a single reaction-intermediate species.
They drew the following conclusions from these simulations:
(1) Increases in the relative effective temperatures of reaction
intermediates due to microwave exposure can increase the
overall reaction rate by orders of magnitude with photon
energies much less than those required to break specific bonds.
(2) The reaction profile does not need to be changed
permanently to produce rate enhancement. (3) Variation of
reaction intermediate energies can give rise to greater overall
reaction rates than either reaction path alone at moderate
conversions. (4) Product/reactant ratios can exceed those
normally attainable during the periodic energy variations of the
reaction intermediates. They proposed that the most significant
influence of microwave enhancement of chemical reactions is
that microwaves can change the reaction profile (or relative
temperatures) instantaneously and often periodically. These
changes are due to the significant differences in microwave
absorption by molecular species, particularly at interfaces.
Microwave exposure can thus increase reaction rates signifi-
cantly by periodically providing a more favorable reaction
coordinate (selective heating: changing the reaction profile).
Microwave enhancement would often be more evident in a
multimode cavity wherein favorable reaction paths might be
present even for short times.
In summary, on the basis of thorough literature search and
analysis, we can get an overall picture that in many cases reports
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Chemical Reviews Review

on the “specific microwave effects” or “nonthermal microwave Table 1. Loss Tangent (tan δ) Values at 2.45 GHz and 20
effects” were based on inaccurate comparisons of the °C17,29 and Boiling Points of Different Solvents
microwave heating with conventional heating; that is, the
boiling point
syntheses were not carried out under exactly the same solvent (°C) tan δ
conditions. Baghbanzadeh et al.17 pointed out that most ethylene glycol ∼198 1.350
scientists agree that in the majority of cases the observed rate ethanol 78 0.941
enhancements should originate from a purely thermal/kinetic 2-propanol 82 0.799
effect, that is, a consequence of the high reaction temperatures methanol 65 0.659
that can be rapidly attained when irradiating polar materials in a 1,2-dichlorobenzene 180.5 0.280
microwave field. No clear and unequivocal evidence has been N-methyl-2-pyrrolidone 202 0.275
found for the existence of “specific microwave effects” or 1-butyl-3-methylimidazolium 0.185
“nonthermal microwave effects”.2 Up to now, a large volume of hexafluorophosphate
experimental data on microwave-assisted syntheses has been acetic acid 118−119 0.174
documented in the literature; however, the detailed mecha- N,N-dimethylformamide 153 0.161
nisms of the chemical reaction, nucleation, and crystal growth 1,2-dichloroethane 84 0.127
of inorganic nanostructures in liquid phase under microwave water 100 0.123
irradiation have still not been fully understood. The existence of chlorobenzene 131 0.101
“nonthermal effects” or “specific microwave effects” of acetone 56−57 0.054
microwave heating has been controversial for years, and the tetrahydrofuran 66 0.047
debate on the exact mechanisms of rate accelerations by dichloromethane 39.8 0.042
microwave heating will still be continuing until unambiguous toluene 111 0.040
conclusions have been reached. Therefore, a large number of hexane 68−69 0.020
carefully designed comparative studies between the microwave
heating and conventional heating are necessary for further preparation of inorganic nanostructures, water (tan δ =
understanding of the microwave heating mechanisms. How- 0.123) and alcohols are good solvents for microwave heating.
ever, the fundamental difficulties facing all comparative studies Ethylene glycol (tan δ = 1.350) has a high boiling point (∼198
between the microwave heating and conventional heating are °C) and reductive ability, allowing relatively high temperatures
the discrepancies of experimental conditions between different for the preparation of inorganic nanostructures in an open
experiments. Unfortunately, in many cases, the microwave- reaction system.
assisted syntheses were often compared to the literature data The dielectric properties of most solvents change signifi-
from those that were performed under completely different cantly with temperature.47 For example, ethanol is a good
conditions such as different reaction temperatures and reaction microwave absorber at room temperature with a tan δ of 0.941.
times, and the conclusions drawn from these comparisons are However, the tan δ of ethanol decreases to 0.270 at 100 °C, and
usually inaccurate and speculative. Therefore, it is strongly further decreases to 0.080 at 200 °C.17 Most organic solvents
recommended that the comparative studies between the such as ethanol are microwave-heated by the dipolar polar-
microwave heating and conventional heating should be ization mechanism, and their ability to absorb microwaves
conducted under exactly identical experimental conditions. decreases with increasing temperature due to decreased bulk
However, one main challenge is that the rapid and unique viscosity and reduced molecular friction. In contrast, the ionic
temperature profiles of the microwave heating are very difficult liquid such as 1-butyl-3-methylimidazolium hexafluorophos-
if not impossible to be duplicated by the conventional heating phate ([bmim][PF6]) is heated by the ionic conduction
methods. As a result, the comparisons of the microwave heating mechanism, so its ability to absorb microwaves increases with
processes with conventional heating ones under exactly the increasing temperature.47 The tan δ of [bmim][PF6] increases
same conditions are inherently challenging. sharply from 0.185 at 20 °C to 1.804 at 100 °C and 3.592 at
1.3. Microwave-Assisted Preparation in Different Solvents
200 °C.17 Therefore, ionic liquids are excellent microwave
absorbers at low and especially at high temperatures, and their
Solvents play important roles in microwave-assisted synthesis in applications in microwave-assisted synthesis of inorganic
liquid phase. Therefore, the solvent is a crucial factor for the nanostructures will be discussed in detail in section 4.
microwave-assisted formation of inorganic nanostructures. The In addition to the single-solvent microwave-assisted syn-
unavoidable choice of a specific solvent for a desired chemical thesis, mixed solvents are also frequently used in the
reaction can have profound economical, environmental, and microwave-assisted synthesis with more freedom of control
societal implications.3 One of the most important properties of over the formation of nanostructures. In the mixed solvent
a solvent is its polarity. The more polar a solvent is, the higher reaction systems, different kinds of solvents can be selected and
its ability to couple with the microwave energy, leading to a volume ratios of solvents can be varied; that is, more
rapid increase in temperature and fast reaction rate.1 The experimental parameters can be adjusted to control the
heating rate and efficiency of the microwaves strongly depend chemical composition, structure, size, and morphology of the
on the properties of the reaction system. The use of excellent product. Different temperatures can be obtained by microwave
microwave absorbing solvents results in high heating rates. The heating in a binary solvent system comprising a polar solvent
solvents used in microwave heating can be classified on the and a nonpolar solvent. For example, for a microwave-assisted
basis of their loss tangent (tan δ): high (tan δ > 0.5), medium phase transfer reaction in a binary system of water and
(tan δ ≈ 0.1−0.5), and low (tan δ < 0.1).29 chloroform, the water phase can reach 100 °C while the
Table 1 shows loss tangent (tan δ) values at 2.45 GHz and chloroform phase can retain a low temperature below its boiling
20 °C17,29 and boiling points of some typical solvents. Among point (∼61 °C), allowing the extraction of the reactants from
the solvents commonly used for the microwave-assisted one phase to the other.
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Chemical Reviews
One clever stragety for microwave heating a nonpolar solvent
is adding a small amount of an excellent microwave absorber
such as an ionic liquid into the nonpolar solvent; in this way,
nonpolar solvents can be used as the media for microwave-
assisted chemistry. An example was reported by Leadbeater et
al.57 on the use of an ionic liquid as an aid for microwave
heating of nonpolar solvents. They found that the addition of a
small quantity of an ionic liquid to a nonpolar solvent greatly
increased the rate and yield of chemical reactions. By adding a
small amount of 1,3-dialkylimidazolium iodide in hexane, the
temperature reached 217 °C after microwave heating at 200 W
for 10 s; in comparison, the temperature was only 46 °C after
microwave heating at 200 W for 10 s in the absence of the ionic
liquid.
1.4. Microwave-Assisted Preparation in an Open Reaction
System
The microwave-assisted preparation of inorganic nanostruc-
tures in liquid phase can be carried out in an open reaction
system under the atmospheric pressure, in which high boiling-
point solvents are usully adopted to enable chemical reactions
at relatively high temperatures. The advantages of the
microwave-assisted preparation in an open reaction system
are relatively simple, safe, and low-cost as compared to those in
an closed reaction system. Among various solvents, polyols with
high boiling points such as ethylene glycol (boiling point ∼198
°C) and glycel (boiling point ∼290 °C) are typical solvents for
carrying out the microwave-assisted preparation in an open
reaction system. The boiling points of many ionic liquids that
are considered as green solvents are very high, and they can also
be adopted. Refluxing is also a choice for performing
microwave-assisted reactions at the boiling point of a solvent
in an open reaction system.
The temperatures for the preparation in an open reaction
system can be selected in the range from room temperature to
the boiling point of the solvent. For example, the reaction
temperatures can be adopted from room temperature to ∼100
°C by using water as the solvent. The reaction temperatures can
be greatly widened from room temperature to ∼198 °C by
using ethylene glycol as the solvent. When glycel is used as the
solvent in an open reaction system, the reaction temperatures
can vary in a wide range from room temperature to ∼290 °C,
even higher than those of many conventional hydrothermal/
solvothermal reactions in a closed reaction system.
However, the range of reaction temperature is narrow by
using low boiling point solvents; for example, the highest
temperature that can be reached is about 65 °C by adopting
methanol as the solvent, at which temperature many chemical
reactions cannot be performed.
1.5. Microwave-Assisted Preparation in a Closed Reaction
System − Microwave-Assisted Hydrothermal/Solvothermal
Method
The microwave dielectric heating is an ideal method for
accelerating chemical reactions and materials synthesis under
pressurized conditions in a closed reaction system. It is possible
to increase the temperature of a reaction system in water or in
an organic solvent higher than the conventional boiling point of
the solvent under pressurized conditions in a closed reaction
system. For example, ethanol has a conventional boiling point
of ∼78 °C, and microwave heating in a closed vessel could
rapidly increase the temperature to 164 °C and a pressure of 12
atm, leading to a thousand-fold acceleration of the reaction
rate.25 In contrast, the reaction temperature usually cannot
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exceed the boiling point of the solvent in an open reaction
system.
In a sealed reaction system, solvents can be brought to
temperatures well above their boiling points by increasing
autogenous pressures resulting from heating. Performing a
chemical reaction in liquid solvents in a closed system is
referred to as “solvothermal processing”, or in the case of water
as the only solvent, “hydrothermal processing”. The hydro-
thermal or solvothermal reactions take advantage of increased
solubility and reactivity of reactants at elevated temperatures
and pressures. The solvothermal/hydrothermal processing
allows many inorganic materials to be prepared at temperatures
substantially below those required by traditional solid-state
reactions. Unlike coprecipitation and sol−gel methods, which
also allow for substantially reduced reaction temperatures, the
products of solvothermal/hydrothermal reactions are usually
crystalline and do not require postannealing treatment. It
should be noted that the pressures generated in a sealed vessel
should always be estimated beforehand, and the pressures
should be monitored during the solvothermal/hydrothermal
experiments for the sake of safety.58 If the pressure is too high
in a closed solvothermal/hydrothermal reaction system, an
explosion will occur.
The traditional hydrothermal and solvothermal syntheses of
inorganic materials in closed reaction systems have been
intensively investigated in the past decades.59 The combination
of the hydrothermal and solvothermal processes with micro-
wave heating has greatly contributed to significant progress in
the rapid synthesis of materials60 due to its remarkably reduced
processing time usually by orders of magnitude as compared to
the traditional hydrothermal/solvothermal processes.61 Micro-
wave-assisted hydrothermal/solvothermal techniques employ
autoclaves made from high-strength polymeric materials that
are transparent to microwaves, but the reaction systems are
rapidly heated to a temperature that is in turn governed by the
pressure.62
In recent years, microwave-assisted hydrothermal or
solvothermal methods have been intensively adopted for the
rapid preparation of inorganic nanostructures in closed reaction
systems at elevated temperatures and pressures. The pressur-
ized environment at an elevated temperature in a closed system
is favorable for many chemical reactions. In a closed reaction
system, the preparation temperatures are not limited by and can
be much higher than the boiling points of solvents. In contrast,
the highest temperature that can be reached in an open reaction
system is determined by the boiling point of the solvent. On
the basis of the solvent used, the preparation in a closed system
is classified as “microwave-assisted hydrothermal” and “micro-
wave-assisted solvothermal” methods. In the microwave-
assisted hydrothermal method, water is used as the only
solvent in a closed system by microwave heating. In contrast,
the microwave-assisted solvothermal method adopts an organic
solvent or mixed solvents in a closed system by microwave
heating.
One striking feature of the microwave-assisted hydrothermal
or microwave-assisted solvothermal synthesis of inorganic
nanostructures is its rapidness as compared to the conventional
hydrothermal or solvothermal method. In the convetional
hydrothermal or solvothermal method, a long period of time
(usually one to several days) is needed. In contrast, the
preparation time can be significantly reduced to minutes
instead of days in the microwave-assisted hydrothermal or
microwave-assisted solvothermal synthesis.
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2. MICROWAVE-ASSISTED PREPARATION OF
NANOSTRUCTURES IN AQUEOUS SOLUTION
Water is the most commonly used solvent for the synthesis of
inorganic nanostructures. About 70% of the earth’s surface is
composed of water, making water the most abundant liquid. In
fact, water was the only solvent available to chemists to carry
out chemical reactions for hundreds of years.3 Water is cheap,
widely available, and environment-friendly. Naturally abundant
water is a good sustainable alternative because of its nontoxic,
noncorrosive, nonflammable nature, and relatively low vapor
pressure as compared to organic solvents.63 Water is also a
polar solvent and a good microwave absorber.
A simplified schematic illustration of the microwave heating
mechanism of water molecules is shown in Figure 3. During the
Figure 3. Water molecules in an alternating electrical field under
microwave irradiation.
microwave heating, polarized water molecules try to orientate
with the rapidly changing alternating electric field; thus heat is
generated by the rotation, friction, and collision of water
molecules. The loss tangents of the solvents, which are related
to the ability of the solvent to absorb microwave energy,
depend on the relaxation times of the molecules. These
relaxation times depend critically on the nature of the
functional groups and the volume of the molecule. Functional
groups capable of hydrogen bonding have a particularly strong
influence on the relaxation time. The relaxation times of
solvents decrease as the temperature of the solvent increases.
Water has a relaxation time of 9 × 10−12 s at 20 °C; that is, it
has a relaxation frequency of ∼18 GHz, and the most effective
conversion of microwave energy into thermal energy will occur
in this frequency region. 25 However, the majority of
commercial and household microwave appliances use a
frequency of 2.45 GHz, which is displaced from this maximum.
It is fortunate that even when the relaxation time is 1 or 2
orders of magnitude different from that which corresponds to
the microwave frequency operating in the cavity, the solvent is
still capable of acting as an effective medium for microwave
dielectric heating because its loss tangent is sufficiently large.
The loss tangent of water at 2.45 GHz and room temperature is
0.123, which is much higher than those at lower frequencies
(0.045 at 900 MHz, 0.001 at 27.12 MHz), and the heating rates
are sufficiently high at this frequency for the food processing
industry.25
The structure of water is influenced when ionic salts are
dissolved in it and the relaxation time decreases at low
concentrations and then increases. It has been proposed that
the presence of the ions causes a hydrogen bonding breakage in
water. Those water molecules that are coordinated to the ions
are rotationally fixed, but those that are not coordinated do not
experience such strong intermolecular hydrogen-bonding
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effects, and consequently in this free state they have lower
relaxation times.64 At higher concentrations, the effects are
reversed, and the relaxation time of water in concentrated salt
solutions is higher than that of pure water, presumably due to a
greater ordering of the water molecules when a large number of
ions are present.25
Because of the advantages of water as the solvent, a large
number of research activities have been devoted to the
microwave-assisted synthesis of inorganic nanostructures in
aqueous solution, and the related experimental data have been
well documented in the literature. In this section, the recent
main progress in microwave-assisted synthesis of inorganic
nanostructures in aqueous solution will be reviewed and
discussed on the basis of the classification of different kinds of
materials.
2.1. Metals, Semimetals, Nonmetals, and Alloys
The preparation of metal nanostructures has been the topic of
intensive research during the past several decades, mainly
because of their unique properties and promising applications
from a technological point of view. The principle for the
formation of metal nanostructures in aqueous solution is based
on the reduction of metallic ions with a reducing reagent under
microwave irradiation. A soluble metal salt is usually used as the
metal source. In many reaction systems, an additive or a
surfactant is also used. The properties of metal nanostructures
depend on their size and morphology, which are determined by
their preparation methods. Nanostructures of noble metals such
as Au, Pt, and Ag are of particular interest due to their close
conduction and valence bands in which electrons move freely.
These free electrons generate surface plasmon bands that
depend on their size and shape. The fascinating color of noble
metal nanocrystals depends on both the size and the shape of
nanocrystals as well as the refractive index of the surrounding
medium.65
In 2005, Tsuji et al.14 published a review article entitled
“Microwave-Assisted Synthesis of Metallic Nanostructures in
Solution”. This article covered the research work made on the
microwave-assisted preparation of metallic nanostructures in
solution before 2005. They discussed some typical examples of
Ag, Au, Pt, and AuPd nanostructures prepared using water-
soluble metal salt, reductant, and surfactant. The metallic
nanostructures with various morphologies including spheres,
polygonal plates, sheets, rods, wires, tubes, and dendrites were
rapidly prepared within minutes by microwave heating. The
morphology and size of metallic nanostructures could be
controlled by adjusting various experimental parameters, such
as the concentration of metal salt, chain length of the surfactant,
solvent, and reaction temperature. Polshettiwar et al.66 reviewed
microwave-assisted preparation of noble metal nanostructures
via reduction of noble metal salts with glucose, sucrose, and
maltose. Recently, Nadagouda et al.13 published a review paper
entitled “Microwave-Assisted Green Synthesis of Silver
Nanostructures”, covering some of their own recent research
work along with others in the production of Ag nanostructures
using microwave irradiation. Readers can also refer to a review
paper by Meng et al. entitled “A Review on Diverse Silver
Nanostructures”.67 In this section, we focus on the research
progress made in the microwave-assisted preparation of metallic
nanostructures in aqueous solution from 2005 upward, which
has been published after the review article by Tsuji et al. in
2005.14
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Among a variety of metals, the microwave-assisted
preparation of Au nanostructures has been most intensively
investigated due to their interesting properties and promising
applications in various fields such as catalysis and biomedicine.
Some examples will be discussed below to highlight the recent
research progress. In almost all cases, HAuCl4 was used as the
gold source, and a reductant was adopted to reduce Au(III) in
aqueous solution. In some reaction systems, an additive or a
surfactant was utilized to adjust the size and morphology of Au
nanostructures.
In a few cases, no reductant was used in the reaction system.
Vargas-Hernandez et al.68 prepared Au nanoparticles using
HAuCl4 in aqueous solution by microwave heating without any
reducing agent. However, due to the absence of any protecting
agent, Au particle aggregation and rapid growth were also
observed. To prevent aggregation, dodecanethiol was added,
and Au nanostructures with well-defined shapes and sizes were
obtained. Two mechanisms were proposed to explain the
reducing ability of water: first, the effect of superheated water
was proposed, and second, a purely electrochemical reaction
was considered to calculate the Gibbs free energy for the overall
redox reaction. The theoretical prediction was in good
agreement with the experimental data. At pH 3, the Gibbs
free energy changed from positive to negative values at
temperatures higher than 100 °C. This method opens the
possibility of producing noble metal nanostructures without
using reducing reagents that are frequently used for metal ion
reduction.
In most cases, a variety of reducing reagents were adopted for
the microwave-assisted preparation of Au nanostructures in
aqueous solution, including NaBH4,69 hydrazine hydrate,70
poly(vinylpyrrolidone) (PVP),71 citric acid or sodium cit-
rate,72−75 α-D-glucose, sucrose, and maltose,76 amino acid,77 2-
naphthol,78 poly allylamine hydrochloride,79 and 2,7-dihydroxy
naphthalene.80 In some reaction systems, an additive or a
surfactant such as cetyltrimethylammonium bromide
(CTAB),74,78,80 PVP,71 PVP/sodium dodecyl sulfate (SDS),73
Triton X-100,77 and pluronic81 was used. Au nanostructures
with various shapes have been reported, such as nano-
particles,69−72,74,77,79,81−88 prisms/cubes/hexagons,76 polygo-
nal/triangular/prisms,78,80 ginger-like nanobranches,73 hexa-
gon-shaped Au nanoplates,75 and triangular/hexagonal struc-
tures.89
Significant effort has been devoted to the control over the
morphology and size of Au nanostructures. For example,
Kundu et al.78 prepared Au nanostructures using HAuCl4·
3H2O, 2-naphthol, NaOH, and CTAB in aqueous solution by
microwave heating for 1−1.5 min. The morphologies of Au
nanostructures (spherical, polygonal, or triangular/prisms, etc.)
were dependent on the molar ratio of surfactant to metal ion
and the concentration of 2-naphthol, and the size and shape of
Au could be tuned simply by varying the molar ratio of the
reactants. Kundu et al.79 prepared aggregates of Au nano-
particles in an aqueous solution containing HAuCl4 and
poly(allylamine hydrochloride) in the presence or in the
absence of Au seed particles by microwave heating for ∼0.5−1
min. The growth of Au nanoparticles could be controlled by
aligning them on the polymeric chain, and Au nanoparticles
subsequently self-assembled to form aggregated nanostructures.
Au nanoparticles were stable for at least 6 months under
ambient conditions. The same research group reported fast
microwave-assisted preparation of Au nanostructures using
CTAB as a surfactant in the presence of 2,7-dihydroxy
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naphthalene as a reducing agent in aqueous solution for 1−
1.5 min, and Au nanostructures with different shapes (spherical,
polygonal, rod, and triangular/prisms) could be obtained by
adjusting the surfactant/metal molar ratio and the concen-
tration of 2,7-dihydroxy naphthalene.80 Wang et al.75 obtained
hexagon-shaped Au nanoplates using HAuCl4 and sodium
citrate in aqueous solution by the microwave-hydrothermal
method. They found that the morphology and size of Au
nanostructures were dependent on both the heating method
and the molar ratio of HAuCl4 to sodium citrate. At a molar
ratio of 5:4, Au hexagonal nanoplates with a large Au (111)
crystallographic facet were obtained. Uppal et al.72 used the
concentration of trisodium citrate to control the size of Au
nanoparticles; smaller Au nanoparticles were obtained with
increasing citrate concentration. Different methods (thermal,
microwave, 254 nm hard ultraviolet light, and sonication), using
reagent solutions with equal concentrations, were used to
prepare Au nanoparticles. The experiments showed marked
differences in the final colloids, with variance in the
monodispersity, size, and shape of Au nanostructures by
different methods. However, the experimental parameters such
as the reaction temperature and reaction time were not the
same in the four methods, making the experimental results
difficult to compare. Kundu et al.71 found that the size of Au
nanoparticles could be controlled through varying the molar
ratio of PVP to Au3+ and by using PVP with different molecular
weights.
The microwave energy is highly efficient and energy-saving in
many chemical processes, which is considered to be environ-
mentally friendly for green synthesis of nanomaterials.4,6,7
Several merits of microwave heating contribute to environ-
mentally friendly synthesis of nanostructured materials,
including short reaction time, low energy consumption, and
high product yield. The microwave-assisted technology can be
combined with other green chemistry strategies to make it
more appealing for green synthesis, which should be greatly
advocated and encouraged because it represents a promising
future research trend.
In recent years, exciting progress has been made in
developing environmentally friendly microwave-assisted ap-
proaches for the preparation of Au nanostructures by using
biocompatible natural materials, for example, bovine serum
albumin (BSA),84,86,87 human serum albumin,87 chicken egg
white lysozyme,85 red wine or grape pomace extract,65 beet
juice,88 and black seed extract.89 These rapid microwave-
assisted green methods provide great potential for applications
of as-prepared biocompatible Au nanostructures in various
biomedical fields. Baruwati et al.65 reported a green microwave-
assisted method for the fabrication of noble metal nano-
particles, such as Au, Ag, Pd, and Pt, using red wine or
preferably grape pomace extract as the only source of green
solvent, reducing agent, and stabilizing agent. Red grape
pomace was chosen as a three-in-one reagent because it
contains numerous polyphenolic compounds that can act as
capping and reducing agents. Microwave irradiation was used to
produce highly crystalline metal nanoparticles within a few
seconds. Because red grape pomace contains much higher
amounts of polyphenolics, they used the major winery waste,
rather than the wine itself, for this high-value product
generation. When the optimized conditions for generating
nanoparticles with red wine were used with pomace, they were
able to produce highly dispersed Au nanoparticles with a
narrow size distribution and a yield of more than 80%. The Au
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nanoparticles were in the size range of 5−10 nm with a
spherical morphology, as shown in Figure 4. Kou et al.88
Figure 4. Transmission electron microscopy (TEM) micrograph of Au
nanoparticles prepared using grape pomace extract at 50 W microwave
power and 60 s exposure time. Reproduced with permission from ref
65. Copyright 2009 Wiley VCH.
reported a rapid microwave-assisted green preparation method
for a variety of noble metal nanoparticles (Ag, Au, Pt, and Pd)
in aqueous solutions using beet juice, an abundant sugar-rich
agricultural product, which served as both a reducing and a
capping reagent at 100 °C for 20 min with a maximum pressure
of 280 psi. Fragoon et al.89 reported a green microwave-assisted
method for the preparation of Au nanostructures using black
seed extract. The shape and size of Au nanostructures were
found to be sensitive to the amount of the extract, and the
reaction temperature had a significant effect on the morphology
of Au nanostructures. The as-prepared Au nanocrystals were
mainly triangular and hexagonal in shape.
Functional folic acid-conjugated Au nanoparticles with sizes
of 15 ± 5 nm were prepared using folic acid, HAuCl4, and
NaOH by a rapid microwave hydrothermal process at 100 °C
for 2 h; the product could target tumor cells overexpressing the
folate receptors, and thus could be used for the sensitive and
selective detection of human HeLa cells.83 Dihydrolipoic acid
capped fluorescent Au nanoclusters were prepared using
HAuCl4, lipoic acid, NaOH, and NaBH4 in aqueous solution
by microwave heating at 180 W for 4 min. The product was
capable of sensing Hg2+ through the specific interaction
between Hg2+ and Au+ on the surface of Au nanoclusters,
and the application of the as-prepared product for monitoring
Hg2+ in living cells was demonstrated.69 Protein-protected Au
nanoclusters were prepared from an aqueous solution of BSA−
HAuCl4−NaOH by microwave heating.86,87 The as-prepared
BSA-protected Au nanoclusters could be used as a fluorescence
enhanced sensor for detection of Ag+ ions with a high
selectivity and sensitivity.86 A similar procedure was also
applied for the preparation of human serum albumin-protected
Au nanoclusters with a strong red emission, which could be
efficiently quenched by nitrogen oxides (NOx), demonstrating
its great potential in determining the intracellular concentration
of NOx.87
In addition to the intensive research on the microwave-
assisted preparation of Au nanostructures, nanostructures of
other noble metals prepared by the microwave-assisted aqueous
solution method, such as Pt,65,88,90,91 Ag,65,70,88,92−111 Au−
Ag,70 Pd,65,88,112 Pd−Pt,113 Cu,106,114 Cu−Ag,106 and Rh,115
have also been reported, and some examples of the related
research work are discussed below.
The microwave-assisted preparation of Ag nanostructures in
aqueous solution has been intensively investigated. Ag
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nanostructures with various morphologies, such as nano-
particles,65,88,94,95,97,99,100,102−104,106−109,111 nanorods and nano-
wires,96,98,101,104 nanocubes,93 pearl-necklace-like and nano-
chains,104,105,108 and prisms,110 have been prepared by the
microwave-assisted methods. In most cases, water-soluble
AgNO3 was adopted as the silver source.
Similar to the research work on microwave-assisted green
preparation of Au nanostructures, it is very encouraging that
some researchers have explored microwave-assisted environ-
mentally friendly preparation methods for Ag nanostructures in
aqueous solution using a variety of biocompatible natural
materials, such as red wine or grape pomace extract,65 beet
juice,88 guava leaf extract,95 leaf extract of saccharum
officinarum (sugar cane),109 starch,94 starch/ascorbic acid,106
amino acids,99 glutathione,102 sucrose and glucose,101,104 and
carboxymethyl cellulose sodium.100 Some examples are
discussed below.
The rapid production of inorganic nanomaterials from plant
extracts under microwave irradiation is a promising green
method for industrial applications. Baruwati et al.65 reported
the microwave-assisted fabrication of Ag nanoparticles using
red wine or preferably grape pomace extract as the only source
of solvent, reducing agent, and stabilizing agent. Kou et al.88
prepared Ag nanoparticles in aqueous solution using beet juice,
an abundant sugar-rich agricultural product, by microwave
heating at 100 °C for 20 min. Ag nanoparticles prepared using
beet juice exhibited higher catalytic activity and durability than
those prepared using NaBH4 in the transformation of 4-
nitrophenol to 4-aminophenol. Chaudhari et al.109 prepared Ag
nanoparticles using fresh leaf extract of Saccharum officinarum
(sugar cane) within a few minutes under microwave irradiation.
Raghunandan et al.95 reported the microwave-assisted rapid
fabrication of Ag nanoparticles with sizes of 26 ± 5 nm from
guava leaf extract in aqueous solution for ∼1.5 min.
Hu et al.99 prepared monodisperse Ag nanoparticles via the
rapid microwave-assisted method in a AgNO3 aqueous solution,
using basic amino acids such as L-lysine or L-arginine as a
reducing agent and soluble starch as a protecting agent, at 150
°C for a very short period of time (only 10 s), and the TEM
micrograph of the product is shown in Figure 5. The as-
prepared Ag nanoparticles had a spherical shape and a mean
particle diameter of 26.3 nm with a standard deviation of 2.1
nm, and were readily redispersed in water, exhibiting a
Figure 5. Typical TEM micrograph of Ag nanoparticles prepared in an
aqueous system using AgNO3 as the silver source, L-lysine as a
reducing agent, and soluble starch as a capping agent via microwave
irradiation at 150 °C for only 10 s. Reproduced with permission from
ref 99. Copyright 2008 American Chemical Society.
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transparent light brown suspension of well-dispersed Ag
nanoparticles (the inset of Figure 5). The aqueous dispersion
of Ag nanoparticles was stable without precipitate for more
than 2 months at room temperature.
Valodkar et al.106 prepared Cu, Ag, and Cu−Ag nanoparticles
by microwave-assisted chemical reduction in aqueous solution
using ascorbic acid as a reducing agent and starch as a
stabilizing agent. Sreeram et al.94 adopted starch as a template
and reducing agent for the microwave-assisted preparation of
Ag nanoparticles with an average size of 12 nm. Filippo et al.101
adopted sucrose as a green reducing reagent for the formation
of Ag nanostructures under pulsed microwave irradiation at 800
W. Ag nanoparticles were formed, and then self-assembled and
fused with each other to form nanowires and further branched
nanowires. In addition, different Ag nanostructures including
spherical nanoparticles, necklace, and nanowires were rapidly
prepared under microwave irradiation from aqueous solutions
of AgNO3 and β-D-glucose.104 Baruwati et al.102 developed a
rapid and green microwave-assisted protocol for the prepara-
tion of Ag nanoparticles ranging from 5−10 nm in size using a
benign antioxidant biomolecule of glutathione as both a
reducing and a capping agent without using any organic
solvent. This method yielded Ag nanoparticles within 0.5−1
min at a power level as low as 50 W. Chen et al.100 employed
carboxymethyl cellulose sodium (CMS) as both a reducing and
a stabilizing reagent. Although the hydrolysis of CMS in
aqueous solution without the help of a catalyst was almost
impossible using the conventional heating method, it could be
achieved by microwave heating. Ag+ ions could be reduced by
the hydrolyzate of CMS to form Ag nanoparticles. The as-
prepared Ag nanoparticles were stable and could be stored at
room temperature for 2 months without any visible change.
Very interesting work has been done for the preparation of
metal nanoparticles using microorganisms; however, this
process was usually slow, but the use of microwave irradiation
will significantly accelerate this process. Saifuddin et al.107
described a novel approach for the preparation of noble metal
nanostructures such as Ag using culture supernatant of Bacillus
subtilis under microwave irradiation in water in the absence of
any surfactant. The reaction mixture was subjected to several
short bursts of microwave irradiation at power output of about
100 W in a cyclic mode (on 15 s, off 15 s, 5−15 cycles). Ag
nanoparticles with sizes in the range of 5−60 nm were
obtained. The formation of nanoparticles by this method is
rapid, requires no toxic chemicals, and the nanoparticles are
stable for several months.
Liu et al.103 prepared highly fluorescent Ag nanoclusters in
the presence of polymethacrylic acid sodium salt in aqueous
solution via microwave heating at 200 W for 70 s. The as-
prepared Ag nanoclusters were monodisperse and uniform with
an average size of 2 nm, and exhibited a strong fluorescence
emission at 575 nm with an excitation at 510 nm. Furthermore,
these nanoclusters were stable, and the fluorescence quenching
did not occur even after 1 month of storage in the dark at 4 °C.
In contrast, when the conventional heating was used, Ag
nanoclusters with a weak fluorescence were not formed until 2
h with unhomogeneous sizes and a low quantum yield. The as-
prepared Ag nanoclusters were explored as a novel fluorescence
probe for the determination of Cr3+ ions with high sensitivity
and selectivity.
Kundu et al.108 reported the microwave-assisted preparation
of Ag nanoparticles in the presence of poly(oxyethylene
isooctyl phenyl ether) (TX-100) and 2,7-dihydroxy naphtha-
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lene as a reducing agent for 1 min. They found that the size of
Ag nanoparticles could be controlled by changing the molar
ratio of Ag+ ion to surfactant, concentration of the reductant,
and pH value of the reaction medium. This method could also
prepare Ag nanochains in a strongly basic medium and at a
lower concentration of TX-100. Kundu et al.93 prepared Ag
nanocubes using an aqueous solution containing AgNO3 and
poly(styrenesulfonate) in the presence of Au seeds by pulsed
microwave heating for 1−2 min. The nanocubes were stable for
at least 2 months under ambient conditions. Ag nanorods were
prepared using silver salt and sodium citrate in the absence of a
surfactant or polymer in water by the microwave-hydrothermal
method.96 Liu et al.98 found that the concentration of Au seeds
played an important role in the formation of Ag nanorods using
AgNO3, sodium citrate, and Au seeds in aqueous solution by a
microwave-assisted process at 100 °C for 10 min. Luo et al.97
prepared dendrimer-protected Ag nanoparticles using AgNO3
and poly(propyleneimine) dendrimer in aqueous solution by
microwave heating at 100 °C for 8 min.
The scaling up of microwave-assisted chemical reactions is
very important for the industrial scale production and
applications of nanostructured materials, and we expect that
this topic will be an important future research trend. Using
continuous flow-type microwave reactors is a promising
strategy, and exciting progress has been made in recent years.
Horikoshi et al.111 reported a continuous-flow reactor system
consisting of a Pyrex pipe (length = 135 mm; internal diameter
= 8 mm) placed horizontally in the microwave waveguide
through which the carboxymethyl cellulose (CMC)/[Ag-
(NH3)2]+ aqueous solution was circulated by a peristaltic
pump, as shown in Figure 6. Microwave irradiation of 1200 W
was obtained from a microwave generator (maximum power
3000 W). In the photograph of Figure 6, the microwaves were
generated from the back toward the reactor with the maximum
of the microwave electric field positioned at the center of the
reactor. A metal mesh closed the waveguide to prevent
microwave leakage and to observe the reaction situation in
Figure 6. (a) Photograph of the continuous flow reactor system for
the microwave-assisted synthesis of Ag nanoparticles; the TEM
micrograph of the as-prepared Ag colloid is also displayed. (b)
Schematic illustration of the overall experimental setup. Concen-
trations: 0.05% w/v CMC, and 60 mM [Ag(NH3)2]+ aqueous
solution. Reproduced with permission from ref 111. Copyright 2010
The Royal Society of Chemistry.
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Figure 7. Experimental setup of the microwave-assisted continuous flow reactor system and a photograph of the microwave cavity part. The quartz
reactor tube is connected with the PEEK sheath, which is designed to resist up to a pressure of 10 MPa. Reproduced with permission from ref 116.
Copyright 2013 American Chemical Society.
the reactor. For maximal heating efficiency, the flow rate of the
peristaltic pump was fixed at 600 mL min−1, and the residence
time of the precursor solution in the microwave reactor was
∼0.7 s. The solution temperature rapidly increased to 100 °C
under microwave irradiation to yield Ag nanoparticles, which
were then collected in the receiver flask and rapidly cooled with
an ice−water bath to prevent any further reaction. The TEM
image in Figure 6 shows the formation of Ag nanoparticles with
a narrow size distribution (0.7−2.8 nm, average size 1.5 nm).
The cartoon in Figure 6 summarizes the reactor setup and the
experimental observations. Interestingly, the internal reactor
walls had no visible evidence of a yellow stain even after 7 min
of microwave irradiation.
The continuous flow-type microwave reactor with a
pressurized function allowing homogeneous heating of the
reaction solution flow is desirable for rapid and scaling up
synthesis of nanostructured materials. This kind of innovative
work has been demonstrated by Nishioka et al.116 They
reported a continuous flow-type single-mode microwave
reactor equipped with an elevated-pressure attachment; this
microwave reactor could form a uniform electromagnetic field
along a tubular reactor (quartz glass, 1.5 mm × 100 mm)
located in the center of a cylindrical microwave cavity, as shown
in Figure 7. This microwave reactor system was characterized
by a variable frequency microwave generator (2.5 GHz ± 200
MHz, 100 W), pressure pump, and a TM010 single-mode cavity
in which a quartz tubular reactor was mounted along the central
axis. The key feature of the microwave reactor system was the
automatic detection and compensation of the resonance
frequency shift. The temperature of the reaction solution was
measured using a radiation thermometer through the open slit
(width, 8 mm) of the cavity. The reaction fluid was pressurized
by a pump and was guided to the quartz reactor tube inlet (1.5
mm × 100 mm). The pressure was controlled manually using a
pressure regulator; it was measured using the pressure gauge.
The quartz reactor tube was connected with the PEEK sheath
as designed to tolerate up to 10 MPa and was sealed with either
a Viton or a Kalrez O-ring. Continuous flows of polar solvents
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including water, EG, and ethanol were heated instantaneously
beyond their boiling points by the application of pressure.
Acceleration of the reaction was exemplified in continuous
synthesis of Cu nanoparticles at the reaction temperature
beyond the boiling point of the solvent of EG at 2 MPa.
As discussed above, among noble metals, the microwave-
assisted preparation of Au and Ag nanostructures has been
intensively investigated. In contrast, other noble metal
nanostructures prepared by microwave heating have been less
reported in the literature. Colloidal Pt nanoparticles were
prepared using an aqueous solution containing H2PtCl6 and 3-
thiophenemalonic acid by microwave heating at 300 W for 8
min, and the particle size could be controlled by the molar ratio
of the reactants.90 By microwave heating an aqueous solution
containing K2PtCl4 and 2-[4-(2-hydroxyethyl)-1-piperazinyl]-
ethanesulfonic acid for only 12 s, Pt nanoclusters with a porous
interconnected nanostructure were obtained.91 Mehta et al.112
prepared Pd nanoparticles using PdCl2, glucose, and poly-
(ethylene glycol) (PEG) as a capping agent in aqueous solution
by microwave heating for only 20 s. Pd@Pt core−shell
nanostructures were prepared in aqueous solution containing
K2PtCl4, PdCl2, and CTAB (pH 9) by microwave heating in a
homemade microwave refluxing synthesis system at 200 W for
3 min, and the morphology of Pd@Pt nanostructures could be
controlled by adjusting the molar ratio of Pt to Pd precursor.113
Pradhan et al.115 reported the microwave-assisted gram quantity
production of one-dimensional (1-D) nanostructures com-
posed of Rh(0) and Rh(I) using CTAB as a reducing agent as
well as a soft template. Reduction of Rh(III) to Rh(0)/Rh(I)
occurred on the glass surface as a result of decomposition of
CTAB upon microwave heating without any other reducing
agent. In contrast, the conventional hydrothermal process
produced only spherical Rh(0) nanoparticles. Liu et al.114
prepared single-crystalline Cu nanowires using CuCl2, ascorbic
acid, and hexadecylamine in deionized water by microwave
heating at 120 °C for 2 h. The as-prepared Cu nanowires had
an average diameter of 50 ± 10 nm and lengths of longer than
10 μm, that is, an aspect ratio of greater than 300. Both ascorbic
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acid and hexadecylamine played important roles in the
morphology and aspect ratio of Cu nanowires. In addition to
noble metal nanostructures, other metal nanostructures have
also been prepared by microwave heating, but less reported. For
example, Sb dendrites composed of well-crystallized nanoflakes
with sizes of 20−40 nm were prepared from an aqueous
solution containing antimony sodium tartrate and Zn powder
in ambient air by microwave heating at 280 W for 30 min.117
Fluorescent Si quantum dots were rapidly prepared using Si
nanowires and glutaric acid via a microwave-assisted process at
185 °C for 15 min. The as-prepared Si quantum dots had good
aqueous dispersibility, high photo- and pH-stability, and strong
photoluminescence, which are promising for the application in
immunofluorescent cellular imaging.118 Zhong et al.119 reported
the microwave-assisted preparation of fluorescent Si nano-
particles using the protein as a hydrophilic ligand. Si nanowires,
which were prepared by an established HF-assisted etching
method, first broke up into Si nanoparticles in aqueous
suspension in a microwave reactor at 180−200 °C. The
resultant Si nanoparticles were further modified with
immunoglobulin G (IgG, a typical protein) as a hydrophilic
ligand by mild microwave heating (30 °C, 5−10 min).
Te nanowires with a diameter of 20 nm and lengths of tens
of micrometers were rapidly prepared using Na2TeO3, aqueous
ammonia, hydrazine hydrate, and PVP in aqueous solution by
the microwave-assisted hydrothermal method at 150 °C for 15
min. The experimental results demonstrated that the amount of
PVP, pH value, a suitable surfactant, and reaction time were key
factors for the formation of high-quality Te nanowires with a
high aspect ratio.120 A microwave-assisted monosaccharide
reduction approach was reported for the preparation of Te
nanotubes with diameters of 50−100 nm and lengths of a few
micrometers using H2TeO3, glucose, and sodium dodecylben-
zenesulfonate in distilled water at 160 °C for 6 h.121 With the
assistance of sugars or their derivatives, 1-D nanostructures of
Te and Se with different sizes were obtained under microwave-
hydrothermal conditions.122
Among nanostructures of nonmetals, the microwave-assisted
preparation of carbon nanostructures has been most intensively
investigated. A variety of carbon nanostructures have been
prepared, including carbon dots,123−130 nanoparticles,131,132
nanospheres,133 and graphene sheets.134−138 Wang et al.123
prepared photoluminescent carbon dots using a carbohydrate
(glycerol, glycol, glucose, sucrose, etc.) and a tiny amount of an
inorganic ion by a one-step microwave method for just a few
minutes. In a typical experiment, glycerol (70% (v/v)) was
mixed with 7.1 mM phosphate solution (pH 7.4) and heated in
a household microwave oven (750 W) for 14 min. The as-
prepared carbon dots exhibited blue, yellow, and red photo-
luminescence under ultraviolet, blue, and green light excitation.
Mitra et al.124 prepared highly fluorescent carbon dots with
average sizes of 1−3 nm embedded in the carbon matrix using
an aqueous solution of PEG, poly(vinyl alcohol) (PVA), and
H3PO4 under microwave irradiation at 750 W for 55−57 s.
Puvvada et al.125 prepared water-dispersible carbon dots
through microwave-assisted pyrolysis of an aqueous solution
of dextrin in the presence of H2SO4 at 800 W for 2.5 min.
Wang et al.126 obtained fluorescent carbon dots using graphite
oxide, candle soot, conductive carbon black, and lampblack in
HNO3 solution by three different heating methods: conven-
tional reflux heating for 12 h, microwave reflux heating for 8 h,
and microwave-hydrothermal treatment at 800 W for 15−60
min. As compared to the conventional reflux heating, the
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microwave-assisted reflux heating and microwave-hydrothermal
method both shortened the reaction time. Carbon dots
prepared using the microwave-assisted techniques exhibited
increased absorption, higher quantum yield, and longer
fluorescence lifetime than those prepared by the conventional
reflux heating. Jaiswal et al.128 used PEG to prepare amorphous
carbon dots with an average size of 4.5 ± 0.9 nm. The synthesis
is based on a rapid one-step microwave-mediated carameliza-
tion of aqueous PEG-200 solution. Irradiation of the aqueous
PEG solution by microwave in a 900 W domestic microwave
oven for 10 min resulted in the formation of golden-yellow
colored solution, indicating the formation of carbon dots.
Experiments with higher than 600 Da molecular weight PEG
did not yield any discernible carbon dots. Prolonging the
microwave irradiation time resulted in the formation of larger
fluorescent carbon dots. Wang et al.129 prepared carbon dots
with a diameter of ∼5 nm from the eggshell membrane ash in
NaOH solution by microwave heating in a domestic microwave
oven for only 5 min. This method is low-cost because the
eggshell membrane is a common protein-rich waste in daily life
and can be obtained easily and cheaply. Jiang et al.127 prepared
carbon dots by microwave heating an amino acid in the
presence of an acid or alkali. Carbon dots with an average size
of 2 nm were obtained from a 20 mL H3PO4 (0.5 mol L−1)
solution containing 2 g of histidine by microwave heating in a
700 W household microwave oven for 160 s. Song et al.130
prepared fluorescent carbon dots with sizes in the range of 2−7
nm from an aqueous solution containing glucose and 4,7,10-
trioxa-1,13-tridecanediamine by microwave pyrolysis at 500 W
for 10 min. Chandra et al.131 prepared carbon nanoparticles
with average sizes of 3−10 nm by microwave heating sucrose as
the carbon source with H3PO4 as an oxidizing agent at 100 W
for 220 s. Zhu et al.132 obtained fluorescent carbon nano-
particles with an average diameter of ∼2.75 nm using PEG-200
and saccharide (glucose, fructose, etc.) in aqueous solution at
500 W for 2−10 min. Cui et al.133 reported the rapid
microwave-hydrothermal preparation of carbon nanospheres
using glucose as the carbon source in aqueous solution at 170
°C for 20 min.
Janowska et al.135 prepared graphene sheets consisting
mostly of mono-, bi-, or few-layer (less than 10 layers) by
exfoliation of expanded graphite in aqueous solution of
ammonia under microwave irradiation, with an overall yield
of ∼8 wt %. Reduction of graphite oxide with ascorbic acid in
aqueous solution under microwave refluxing within 30 min was
also reported for production of graphene sheets.134 Long et
al.137 prepared water-dispersible polymer-grafted graphene
sheets with a thickness of about 3.5 nm from a reaction system
containing graphite oxide, NaOH, acrylamide monomer,
azodiisobutyronitrile, and hydrazine hydrate by microwave
heating involving prereduction, grafting, and postreduction.
Polyacrylamide chains were rapidly grafted onto the graphene
sheets via free-radical polymerization under sequential micro-
wave irradiations. Vadahanambi et al.138 reported a rapid
microwave route to graphene nanosheets and those decorated
with metal nanoparticles (Fe, Pt, and Pd) by using a chemical
foaming agent (azodicarbonamide), an oxidizer (H2O2), and a
radical initiator (ammonium peroxydisulfate). Under micro-
wave irradiation, an intercalated foaming agent between
graphite oxide layers led to rapid exfoliation, accompanied by
lightening and release of gases. Sufficient care must be taken
because this microwave reaction may cause violent explosions.
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Pt decorated graphene exhibited a highly sensitive biosensor for
glucose even in a neutral phosphate buffer solution.
2.2. Metal Oxides
Considerable effort has been devoted to microwave-assisted
synthesis of nanostructures of various metal oxides due to their
interesting properties, high stability, and wide applications in
many fields. In many cases of microwave-assisted synthesis of
metal oxide nanostructures, a water-soluble metal salt is used as
the metal source, an alkaline reagent is used to create an
alkaline environment, and an additive or a surfactant is often
adopted to control the morphology and size of the product.
Nanostructures of metal oxides with various morphologies have
been prepared in aqueous solution by microwave-assisted
methods; some examples of metal oxides include MgO,139
PdO,140 PtO2 ,141 ZnO,142−154 SnO,155,156 SnO 2,157−161
TixSn1−xO2,162 α-Fe2O3,163−170 γ-Fe2O3,171 Fe3O4,163,172−175
Co 3 O 4 , 176−181 CuO, 182−189 Mn 3 O 4 , 190 MnO 2 , 191−196
TiO 2 , 197−213 TiO 2−x C x , 214 ZrO 2 , 215−219 WO 3 , 220−223
MoO3,224 CeO2,53,225−233 Nd2O3,234 Y2O3,235 (Y,Gd)2O3,236
V2O5,237 MWO4 (M = Ca, Sr, Ba, Fe, Co, Ni, Mn, Zn, Ag/
In),238−244 Bi2WO6,245−247 NaY(WO4)2,248 Y3Al5O12,249−251
Zn2SnO4,252 ZnGa2O4,253,254 MFe2O4 (M = Mg, Zn, Ni, Mn,
Co),255−260 MAl2O4 (M = Zn, Co),261−263 BiFeO3,264−266
Bi2Fe4O9,265 Bi1.8Y1.2Fe5O12,267 MnCo2O4,268 MTiO3 (M = Ba,
Sr, Pb),45,269−278 Li4Ti5O12,279 K2Ti6O13,280 MMoO4 (M = Ba,
Ca), 281,282 γ-Bi 2 MoO 6 , 283 Cd 2 Ge 2 O 6 , 284 Na 2 Ta 2 O 6 , 285
SnNb2O6,286 and MVO4 (M = Bi, Ce, Y, La).287−291
ZnO nanostructures with various morphologies have aroused
much interest due to their interesting properties and wide
applications in various fields. Hu et al.142 prepared linked ZnO
rods with various morphologies such as bipods, tripods, and
tetrapods using Zn(NO3)2·6H2O and hexamethylenetetramine
(HMTA) in aqueous solution by microwave heating at 90 °C
for 2 min. The oriented attachment mechanism was proposed
for the formation of linked ZnO rods. Unalan et al.143 reported
the rapid synthesis of ZnO nanowires on various substrates
(such as poly(ethylene terephthalate), silicon, and glass) using a
commercial microwave oven. Vertical ZnO nanowires were
grown by dipping the substrates in an aqueous solution of
Zn(NO3)2·6H2O and HMTA under microwave irradiation at
different powers (120, 385, and 700 W) at atmospheric
pressure for 1−30 min. The average growth rate of ZnO
nanowires was as high as 100 nm min−1, depending on
microwave power. Cho et al.152 prepared density-controlled
ZnO nanorod arrays on a flexible Teflon substrate using
inductively coupled plasma etching with anodic aluminum
oxide (AAO) membranes in an aqueous solution containing
Zn(CH3COO)2·2H2O and ammonia under microwave irradi-
ation at 90 °C for 40 min. The average interpore distances of
the Si surface etched with an AAO membrane anodized in 0.3
M oxalic acid and an AAO membrane anodized in 0.1 M
phosphoric acid were ∼100 and ∼450 nm, respectively. During
the microwave irradiation, ZnO nanorods grew from Si pores.
Thus, the density of ZnO nanorods could be controlled by
changing the interpore distance of the AAO membrane mask.
ZnO porous nanoplates were synthesized using an aqueous
solution containing zinc salt and an alkali (urea or ammonia)
through microwave irradiation and subsequent thermal heating
of the nanoplate precursor.144,150 ZnO nanotubes were
prepared using an aqueous solution containing Zn(NO3)2·
6H2O and urea under microwave irradiation at 180 W for 40
min.154 ZnO nanostructures including nanorods, nanocandles,
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nanoneedles, nanodisks, and nanonuts were obtained at 90 °C
with a low microwave power (∼50 W) and a subsequent aging
process. In addition, more complex ZnO structures including
ZnO bulky stars, cakes, and jellyfishes were also obtained.153
ZnO micro-/nanostructured materials with different morphol-
ogies were synthesized using aqueous solutions containing
ZnCl2 and ammonia via the microwave-hydrothermal method
for 1−2.5 min, and fork-like, hollow shuttle-like, multiwalled
tube-like, flower-like, and lamella-like morphologies were
obtained by simply varying the reaction time.145 Hexagonal
ZnO nanostructured flowers composed of spear-shaped
nanorods with diameters of 50 nm were synthesized from an
aqueous solution containing a 1:15 molar ratio of Zn-
(CH3COO)2·2H2O to KOH under 180 W microwave
irradiation for 20 min.147 ZnO nanostructures with various
morphologies (nanoparticles, nanorods, and flowers) were
synthesized using Zn(CH3COO)2·2H2O, NaOH, and guanidi-
nium carbonate or acetyl acetone in aqueous solution via the
fast microwave-assisted method for 2 min.148 ZnO rods with
hierarchical nanostructures were prepared using the micowave-
hydrothermal method. The thorn-like nanostructures were
grown on the surface of rods in high density with lengths from
∼10 to 80 nm.149
Iron oxides are important functional materials and have wide
applications in many fields. Considerable effort has been
devoted to microwave-assisted synthesis of iron oxide
nanostructures, and some examples are discussed below.
Amorphous Fe2O3 nanoparticles with sizes of ∼3−5 nm were
synthesized by pulsed microwave heating an aqueous solution
containing FeCl3·6H2O, PEG-2000, and urea at 650 W for 10
min.292 α-Fe2O3 nanoparticles of 23−25 nm in diameter were
prepared using 0.02 M Fe(NO3)3·9H2O solution by a
microwave-hydrothermal process at 100 °C for 4 h.164 α-
Fe2O3 nanoparticles with sizes of ∼5 nm were prepared using
Fe(NO3)3 and urea in aqueous solution by a microwave-
assisted hydrothermal route at 120 °C for 30 min.166 α-Fe2O3
nanoparticles were prepared using FeCl3, PEG, N2H4·H2O, and
H2O2 in aqueous solution by rapid microwave heating at 100
°C for 10 min. The morphology of α-Fe2O3 was affected by the
heating method. Ellipsoidal α-Fe2O3 nanoparticles formed
following the oriented attachment mechanism by microwave
heating, while a mixture of irregular α-Fe2O3 nanoparticles and
rods was obtained by oil bath.163 α-Fe2O3 nanorods with an
average diameter of ∼60 nm were prepared using FeCl3·6H2O
and PVP in aqueous solution through the microwave-assisted
hydrothermal method at 120−180 °C for 2 h.165 Hu et al.168
prepared α-Fe 2 O 3 nanorings using FeCl 3 ·6H 2 O and
NH4H2PO4 in aqueous solution by a microwave-hydrothermal
process at 220 °C for 25 min. The TEM micrographs of the as-
prepared α-Fe2O3 nanorings are shown in Figure 8; the sample
consisted of more than 90% ringlike structures. Figure 8B
shows a high-magnification TEM image of a single α-Fe2O3
nanoring with a circular shape, and its corresponding electron
diffraction pattern (Figure 8C) indicates that the nanoring was
single-crystalline. α-Fe2O3 nanorings had an average outer
diameter of ∼100 nm and inner diameters ranging from 20 to
60 nm. Because the hydrolysis of Fe3+ ions is pH-dependent,
and the equilibrium between phosphate anions and Fe3+ ions
determines both the availability of free phosphate ions and the
dissolution degree of solid α-Fe2O3, the growth of α-Fe2O3 can
be thermodynamically controlled by adjusting the reactant
concentration. The sensors made of α-Fe2O3 nanorings
exhibited high sensitivity not only for biosensing of H2O2 in
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Figure 8. (A) Low-magnification TEM image of α-Fe2O3 nanorings;
(B) high-magnification TEM image of a single α-Fe2O3 nanoring; and
(C) electron diffraction pattern indicating the single-crystalline nature
of the nanoring. Reproduced with permission from ref 168. Copyright
2007 Wiley-VCH.
a physiological solution but also for gas-sensing of alcohol
vapor at room temperature.
Hu et al.167 reported the rapid microwave-hydrothermal
synthesis of monodisperse α-Fe2O3 nanocrystals using an
aqueous solution containing FeCl3 and NH4H2PO4 at 220 °C
for 10−25 min, and a variety of morphologies, including
ellipsoids/spindles with aspect ratios ranging from 1.1 to 6.3,
nanosheets, nanorings, and spheres, were obtained. A micro-
wave-assisted hydrothermal process was adopted for the fast
synthesis of α-Fe2O3 hierarchically nanostructured architectures
using an aqueous solution containing K3[Fe(CN)6]. It was
found that the reactant concentration and reaction temperature,
instead of the reaction time, had a great influence on the
morphology of the product. Several kinds of nanostructures,
such as nanoparticles, dendritic crystals, plates, and self-
organized nanorods, could be obtained under different
experimental conditions.169 α-Fe2O3 hierarchical microspheres
formed by self-assembly of 30−50 nm nanoparticles were
obtained using FeCl3·6H2O, urea, and polyacrylamide in
aqueous solution by microwave refluxing for 20 min, followed
by thermal treatment at 550 °C for 4 h.170 Sreeja et al.171
prepared γ-Fe2O3 nanoparticles with an average particle size of
10 nm from an aqueous solution containing FeSO4·7H2O,
FeCl3·6H2O, and NaOH under microwave-hydrothermal
conditions at 150 °C for 25 min.
Fe3O4 is an important magnetic functional material and has
wide applications in many fields. Fe3O4 nanostructures are
usually obtained using water-soluble iron(III) salt or salts of
iron(III) and iron(II) and a reductant in aqueous solution
under microwave irradiation. In some methods, an additive or a
surfactant is used. Miao et al.173 prepared Fe3O4 nanoparticles
using a rusty iron foil (Fe and Fe2O3) in deionized water in the
absence of any alkali, acid, or surfactant in a household
microwave oven at 700 W for 30 min. The as-prepared Fe3O4
nanoparticles with sizes ranging from 20 to 60 nm attached to
the iron surface, which were separated by ultrasonic and
magnet. The as-synthesized Fe3O4 nanoparticles exhibited a
saturation magnetization value of 51.3 emu g −1. Fe3O4
nanoparticles were prepared using an aqueous solution
containing FeCl3, FeSO4, and ammonia by the microwave-
assisted method.172 In another work, Fe3O4 nanoparticles were
prepared using FeCl3, N2H4·H2O, and PEG in aqueous solution
by microwave heating at 100 °C for 10 min.163 Zhou et al.174
synthesized Fe3O4 hexagonal nanoplates with an average edge
length of 80 nm using FeSO4·7H2O, CH3COONa·3H2O, citric
acid, NaOH, and NaH2PO2 in aqueous solution via a facile
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microwave-assisted route. The morphology and size of the
product could be varied by adjusting the reaction time,
microwave power, and concentrations of reactants, and citric
acid was found to play a key role in the formation of Fe3O4
nanoplates. Muraliganth et al.175 adopted a microwave-
hydrothermal approach to synthesize single-crystalline Fe3O4
nanowires in the presence of PEG as a soft template in aqueous
solution at 150 °C within 15 min. Milosevic et al.293 obtained
magnetic nanorods of a mixture of Fe3O4, γ-Fe2O3, and β-
FeOOH by microwave-assisted hydrothermal reduction at 100
°C using β-FeOOH nanorods as the iron source and template
and hydrazine as a reductant, and the size and shape of the
product could be controlled through adjusting experimental
parameters. Wu et al.294 reported the fast microwave-assisted
synthesis of lamellar sodium/potassium iron oxide nanosheets
consisting of two-dimensional iron oxide building blocks
separated by the intercalated sodium/potassium ions using
FeSO4·7H2O, Na2S2O3·5H2O, NaOH, and KOH in aqueous
solution at 180 °C for 5 min.
The microwave-assisted method has also been applied in the
rapid synthesis of cobalt oxide nanostructures. For example, Ma
et al.176 prepared Co3O4 nanocrystals using an aqueous solution
containing C4H6CoO4·4H2O and NaOH by the microwave-
hydrothermal method at 200 °C for 1 h. Li et al.177 prepared
spherical or cubic Co3O4 nanoparticles (10−20 nm) using
cobalt salt, 3-mercaptopropionic acid, and NaOH in aqueous
solution by microwave heating at 100−140 °C within 10 min.
Spherical nanoparticles were obtained at a lower temperature;
however, cubic nanoparticles formed at a higher temperature.
Lai et al.178 prepared Co3O4 nanorods by the microwave-
assisted synthesis of cobalt hydroxide carbonate nanorods from
a solution containing Co(NO3)2·6H2O and urea under 500 W
microwave irradiation for 3 min, followed by calcination at 400
°C. Al-Tuwirqi et al.180 synthesized Co3O4 nanostructures
using Co(CH3COO)2, NaOH, and citric acid through the
microwave-assisted hydrothermal method at 200 °C for 30 min.
Wang et al.181 prepared Co3O4 nanowires with a porous
structure constructed by self-assembly of nanocrystals by a
microwave-assisted process (110 °C, 1 h) combined with a
thermal transformation process (350 °C, 2 h, air). Meher et
al.179 investigated the effect of microwave heating on the
morphology, optical, magnetic, and pseudocapacitance behavior
of Co3O4. They found the difference in dimensionality of
Co3O4 nanowires by employing the microwave-assisted reflux
(120 °C, 15 min) and conventional reflux (120 °C, 12 h) using
Co(NO3)2·6H2O, P123, and urea in aqueous solution. The
Co3O4 sample obtained by the conventional reflux consisted of
randomly distributed thin nanowires, while the microwave
reflux method generated higher-dimensional and arranged
Co3O4 nanowires.
Nanostructures of other metal oxides have also been rapidly
synthesized by the microwave-assisted method. Qiu et al.187
prepared CuO nanostructures in aqueous solution of Cu-
(CH3COO)2/urea or Cu(NO3)2/urea at 150 °C for 30 min via
a microwave-assisted hydrothermal process. In the Cu-
(CH3COO)2/urea reaction system, CuO nanoparticles formed
and assembled into spheroidal microspheres. However, CuO
nanorods formed and assembled into flower-like structures in
the Cu(NO3)2/urea aqueous solution. This study shows that
the anions in the reaction system have an influence on the
morphology of the product. Liang et al.182 synthesized single-
crystalline CuO nanosheets with a monoclinic structure from a
layered precursor, copper(II) acetate hydroxide, in 0.1 M
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NaOH aqueous solution by microwave heating at 100 °C for
5−45 min, and the layered precursor was synthesized using
Cu(CH3COO)2·H2O and NaOH in EG by microwave heating
at 140 °C for 5 min. Moura et al.188 prepared CuO nanoplates
using CuCl2·2H2O and NaOH in aqueous solution without any
surfactant by a microwave-hydrothermal process at 130 °C for
30 min. Single-crystalline CuO nanoleaves with an average
thickness of ∼10 nm were synthesized by microwave heating an
aqueous solution containing copper salt and NaOH at 80 °C
for 10 min or 100 °C for 20 min.189 CuO hierarchical hollow
nanostructures constructed by self-assembly of nanorods were
synthesized using an aqueous solution containing Cu-
(CH3COO)2·H2O and CO(NH2)2 by microwave heating at
80 °C for 30 min.184 Urchin-like CuO structures composed of
spiny leaves were synthesized using CuCl2·2H2O and Na2CO3
in aqueous solution by microwave heating at 30% of maximum
power (800 W) for 20 min.185 Volanti et al.186 reported the
rapid microwave-assisted hydrothermal synthesis of sea urchin-
like CuO architectures, and they proposed a growth mechanism
that involved a mesoscale self-assembly followed by fusing the
adjacent crystallites.
Polshettiwar et al.295 fabricated nanostructured metal (Fe,
Co, Mn, Cr, Mo) oxides from the precursor K4Fe(CN)6,
K3Co(CN)6, K3Mn(CN)6, K3Cr(CN)6, or K3Mo(CN)8 in
aqueous solution under microwave-hydrothermal conditions at
180 °C for 3 h without using any reducing or capping reagent.
The size and shape of the final product could be tailored by
varying the experimental conditions. Different morphologies
including octahedra, spheres, triangular rods, pines, and
hexagonal snowflakes were obtained. α-Fe2O3 structures self-
assembled into pine and hexagonal snowflake-like morpholo-
gies.
Mn3O4 polyhedral nanocrystals were prepared using an
aqueous solution containing Mn(CH3COO)2 and (CH2)6N4 by
microwave heating. Cubic and rhombohedral shapes of Mn3O4
with edge lengths in the range of 15−40 nm were obtained at
80 °C for 1 h. Mn3O4 nanocrystals grew following the Ostwald
ripening mechanism with increasing reaction time.190 γ-MnO2
nanoplates were synthesized using KMnO4 and Mn(NO3)2 in
aqueous solution under microwave irradiation at 160 °C for 30
min.191 A rapid microwave-assisted hydrothermal process was
reported for the preparation of cryptomelane-type manganese
oxide octahedral molecular sieve (OMS-2) nanostructures
using an aqueous solution containing K2SO4, K2S2O8, and
MnSO4·H2O at temperatures of 80−200 °C with a hold time of
10 s to 30 min. In contrast, up to 4 days was required in a
conventional hydrothermal reaction. The OMS-2 nanowires
were produced from thin nanoflakes with increasing reaction
temperature.195 Birnessite-type MnO2 nanospheres with 70−90
nm in diameter were synthesized using KMnO4, MnSO4·H2O
in deionized water by the microwave-hydrothermal method at
75 °C for 30 min at a low pressure.196 Du et al.192 synthesized
δ-MnO2 with a layered structure using an aqueous solution
containing KMnO4 and HCl by the microwave-assisted
hydrothermal method at 110 °C for 1 h, the product consisted
of flower-like microspheres, and they were formed by self-
assembly of nanosheets as the building blocks with thicknesses
ranging from 5 to 10 nm. Li et al.193 synthesized birnessite
flower-like and α-type tubular MnO2 nanostructures from an
aqueous solution containing KMnO4 and HCl by the
microwave-assisted hydrothermal method for 25 min, and the
crystal phase and morphology could be controlled by adjusting
the reaction temperature. Truong et al.194 synthesized δ-MnO2
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microflowers consisting of assemblies of nanosheets, α-MnO2
nanowires, and α-MnO2 nanotubes through a microwave-
assisted hydrothermal reduction of KMnO4 in the presence of
HCl in aqueous solution.
TiO2 nanostructured materials are very important due to
their technological importance and wide applications in many
fields such as photocatalysis. Baldassari et al.197 prepared
anatase TiO2 nanoparticles by microwave-assisted hydrolysis of
TiCl4 in a diluted acidic aqueous solution. The product was
almost completely crystallized in a short reaction time of 30
min under microwave-hydrothermal conditions. The presence
of a small amount of sulfuric acid was necessary to obtain a
pure anatase phase because sulfate prevented the crystallization
of a trace amount of brookite. TiO2 nanoparticles were
arranged in spherical aggregates in the presence of 1% sulfuric
acid, while less aggregated nanoparticles were obtained with
0.1% sulfuric acid. They also prepared rutile TiO2 nanoparticles
from an aqueous solution of TiCl4 by a microwave-hydro-
thermal process at different temperatures (100−160 °C) for 5−
120 min, and the addition of PVP to the reaction system
produced needle-shaped crystals.198 Similarly, TiO2 nano-
particles were also obtained from an aqueous solution
containing TiCl4/HCl,199 TiOCl2,200 TiOCl2/urea,201 or
(NH4)2TiF6/H3BO3202 by microwave heating in a short period
of time. The microwave-assisted hydrothermal method was
employed to prepare TiO2 nanoparticles with sizes of ∼5 nm
from commercial K2Ti4O9 particles without using any organic
species at 190 °C for 10 min.203
Rutile TiO2 mesocrystals assembled with ultralong nanowires
were prepared by the microwave-assisted hydrothermal
approach using TiCl3 as the only reactant in aqueous solution
at 200 °C for only 1 min.208 Suprabha et al.205 prepared TiO2
nanostructures with different morphologies, particle sizes, and
surface areas using TiCl3 as the titanium source and different
precipitating agents at different pH values under microwave
irradiation. The morphology of the product could be controlled
by changing the pH value of the solution, and various
morphologies were obtained including cubical, spherical, and
rod shapes. Zheng et al.204 reported the microwave-assisted
hydrothermal synthesis of anatase TiO2 nanocrystals with
tunable percentage of the reactive (001) facet from an aqueous
solution of tetrabutyl titanate and HF at 200 °C for 30 min.
They found that the shapes of TiO2 nanocrystals evolved from
nanosheets to truncated octahedral bipyramids, resulting in a
decrease in the percentage of the exposed (001) facet from 71%
to 23% with increasing amount of water. Commercial TiO2
nanoparticles (P25) were also adopted for the synthesis of
anatase TiO2 nanowires with diameters of 5−10 nm in KOH
aqueous solution by microwave heating combined with
calcination.207 TiO2 nanotubes with diameters of 8−12 nm
were synthesized using TiO2 of either anatase or rutile or mixed
phases and NaOH in aqueous solution by microwave heating at
195 W for 90 min.209 Titanate nanotubes with inner diameters
of ∼5−9 nm were prepared in a high yield (>90%) using an
aqueous solution containing anatase TiO2 and 40% (w/w)
NaOH by pulsed microwave heating for 6 h.296 Sitthisang et
al.210 prepared undoped and C-doped anatase TiO2 nano-
particles from a Ti precursor, such as Ti ethoxide, Ti
isopropoxide, or Ti oxysulfate, and a carbon source (glucose,
sucrose, or cyclodextrin) in deionized water by a microwave-
hydrothermal process in the temperature range of 140−180 °C
for 1 or 2 h. Anatase nanoparticles with sizes of 4−17 nm were
obtained in all cases with specific surface areas in the range of
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151−267 m2/g. Yin et al.211 prepared nitrogen-doped titania
(TiO2−xNy) nanoparticles by a microwave-assisted hydro-
thermal process. Glaspell et al.212 synthesized TiO2 nano-
particles doped with 1%, 5%, or 10% transition metal (Co, Fe,
and Ni) using metal salts in aqueous solution by microwave
heating.
SnO nanoparticles with sizes less than 30 nm were
synthesized by a microwave-assisted solution process, in
which amorphous oxy-hydroxy precipitate of Sn2+ was
crystallized by microwave heating. It was found that microwave
heating selectively accelerated SnO crystallization but not the
concurrent Sn2+ oxidation, which otherwise prevailed in the
conventional thermal heating process.155 Pires et al.156 prepared
SnO powders with different morphologies using SnCl2·2H2O as
the tin source by a microwave-assisted hydrothermal process.
By changing the hydrothermal processing time, temperature,
type of mineralizing agent (NaOH, KOH, or ammonia), and its
concentration, SnO crystals with a plate-like shape and
thicknesses varying from 30 nm to 2 μm could be obtained.
Yoshinaga et al.158 prepared SnO2 nanoparticles with sizes of
∼5 nm using SnCl4·5H2O as the only starting reagent in
aqueous solution by microwave heating at 100 °C for 5 min.
The specific surface area of microwave-synthesized SnO2
nanoparticles was about 10 times larger than that of the
SnO2 specimen synthesized by the conventional heating
method. SnO2 nanoparticles were investigated as a rechargeable
electrode material, and the initial lithium insertion capacity was
significantly higher than that of a specimen synthesized by the
conventional heating method. SnO2 nanoparticles with sizes of
several nanometers were prepared from SnCl4/urea or SnCl4/
HCl or SnCl4/HCl/alkali (urea or ammonia) in aqueous
solution by microwave heating.157,159,160 Porous SnO2 nano-
tubes were synthesized using SnCl4 and glucose in aqueous
solution by a rapid microwave-assisted hydrothermal process at
150 °C for 30 min followed by annealing in air, and SnO2
nanotubes were formed by interconnected nanocrystals with
sizes of ∼8 nm.161 Solid solutions of TixSn1−xO2 were prepared
from a solution containing TiCl3 and SnCl4 by a microwave-
assisted hydrothermal process at 200 °C for 10 min, and the
difference in the formation rate of TiO2 and SnO2 could be
effectively reduced by microwave heating under the constant
power mode, resulting in the precise control of the solid
solution composition.162
Rizzuti et al.216 prepared ZrO2 nanoparticles with sizes of ∼8
nm from an aqueous solution of ZrOCl2·8H2O by the
microwave-hydrothermal method, and the as-prepared ZrO2
nanoparticles aggregated to form big aggregates of ∼50 nm.
Bondioli et al.215 prepared ZrO2 nanoparticles with sizes of 10−
20 nm using ZrOCl2·8H2O and NaOH in aqueous solution
under microwave-hydrothermal conditions at 194 °C for 2 h,
and it was found that the tetragonal polymorph increased with
increasing NaOH concentration and reached the maximum
value by using 1 M ZrOCl2·8H2O. Bellon et al.217 reported the
microwave-forced hydrolysis preparation of ZrO2 consisted of
aggregates of small primary nanoparticles using ZrCl4 solution
at 180 °C, and the obtained solution was colloidally stable for
more than 6 months without sedimentation. Bondioli et al.218
used the microwave-assisted hydrothermal method for the
synthesis of Pr-doped ZrO2 nanoparticles with an average size
of 7.9 nm using ZrOCl2·8H2O, Pr(NO3)3, and NaOH in
aqueous solution (pH 9) at 14 atm for 2 h. Rizzuti et al.219
reported that NaOH-based hydrolysis of zirconyl chloride in a
solution containing Ca(NO3)2 followed by a microwave-
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hydrothermal process at 220 °C for 30 min resulted in calcia-
stabilized tetragonal ZrO2 nanoparticles with sizes of about 7
nm.
Hariharan et al.220 reported the synthesis of WO3 nano-
particles using H2WO4, NaOH, PEG, and HCl (pH 1) by
microwave heating at 180 W for 10 min. Both samples prepared
with and without the surfactant crystallized in the ortho-
rhombic structure corresponding to WO3·H2O. However,
subsequent annealing under identical conditions (600 °C/air/
6 h) led to significantly different products, that is, monoclinic
W17O47 from the surfactant-free sample and orthorhombic
WO3 from the PEG-assisted sample. Sun et al.221 prepared
WO3·2H2O nanospheres using Na2WO4·2H2O and L-(+)-tar-
taric acid by a microwave-hydrothermal process at 320 W for
20 min, and the morphology of WO3·2H2O nanostructures was
dependent on the concentration of L-(+)-tartaric acid, which
played an important role in the formation of WO3·2H2O
nanospheres. Phuruangrat et al.222 prepared hexagonal WO3
nanowires with diameters of 5−10 nm in an aqueous solution
containing (NH4)2SO4 and Na2WO4 by the microwave-assisted
hydrothermal method at 150 °C for 3 h. Sungpanich et al.223
synthesized WO3 nanoplates using Na2WO4·2H2O and citric
acid in deionized water by a microwave-hydrothermal process
at 270 W for 0.5−3 h. Wei et al.224 prepared MoO3 nanoflowers
with an orthorhombic structure directly grown on a Si substrate
by a microwave-hydrothermal process at 90 °C for 2 min. The
nanoflowers consisted of nanobelts with tens of nanometers in
thickness, tens to several hundreds of nanometers in width, and
up to ten micrometers in length.
Corradi et al.225 prepared CeO2 nanoparticles with diameters
of 4−5.8 nm from the reaction between (NH4)2Ce(NO3)6 and
NaOH in aqueous solution under microwave-hydrothermal
conditions at 13.4 atm for 5 min. Araújo et al.229 synthesized
CeO2 nanoparticles using an aqueous solution containing
Ce(NO3)2·6H2O and NaOH by the microwave-assisted
hydrothermal method at different temperatures for 16 min,
and the morphology of the product could be varied by adjusting
the hydrothermal temperature. The product synthesized at 80
°C consisted of spherical nanoparticles with sizes of ∼5 nm,
while a mixture of spherical and rod-like nanostructures were
obtained at 120 °C, and nanorods with an average diameter of
10 nm formed at 160 °C. CeO2 nanoparticles were prepared
using an aqueous solution containing (NH4)2Ce(NO3)6, a weak
alkali (CH3COONa or HMTA or ammonia), and PEG under
microwave irradiation.226−228 Natile et al.230 prepared CeO2
nanostructured powders by two different synthetic routes: two
samples were obtained by precipitation from a basic solution of
cerium nitrate at 250 and 650 °C, respectively, and the third
one was prepared by microwave-assisted hydrolysis in aqueous
solution using [(NH4)2Ce(NO3)6], CH3COONa, and PEG at
90 °C (350 W) for 10 min. A broad particle size distribution
was observed for CeO2 nanoparticles obtained by precipitation
(8.0−15.0 nm), and smaller nanoparticles (around 3.3−4.0
nm) with a narrow particle size distribution were obtained by
microwave heating.230 Gao et al.231 adopted the microwave-
hydrothermal method for the fast synthesis of CeO 2
nanostructures, and the average sizes of CeO2 nanoparticles
could be adjusted from ∼1.6 to 20 nm. By changing the cerium
source and amount of aqueous ammonia, CeO2 nanorods could
be obtained.
Microwave-assisted methods are also capable for the
preparation of rare earth doped CeO2 nanostructures in
aqueous solution in a short period of time. Godinho et al.53
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prepared Gd-doped CeO2 nanoparticles using Ce(NO3)3·
6H2O, Gd2O3, a small amount of HNO3, and ammonia in
aqueous solution by microwave-hydrothermal treatment at 130
°C for 30 min. Bondioli et al.232 synthesized Pr-doped CeO2
nanoparticles with sizes of ∼25−30 nm using (NH4)2Ce-
(NO3)2, Pr(NO3)3·6H2O, and ammonia in aqueous solution by
a microwave-assisted hydrothermal route for 1 h. Prado-Gonjal
et al.233 obtained Sm- and Gd-doped and undoped CeO2
nanoparticles from aqueous solutions containing corresponding
metal nitrates and KOH under microwave-hydrothermal
conditions at 200 °C for 30 min.
de Moura et al.235 reported the microwave-assisted synthesis
of Y2O3:Eu3+ nanorods and nanoplates through thermal
decomposition of Y(OH)3 precursors. The precursors were
prepared using Y(NO3)3·8H2O, Eu2O3, and HNO3 (the final
pH value of 12.5 was adjusted using a NaOH solution) under
microwave-hydrothermal conditions at 140 °C for 10, 20, and
40 min. Y2O3 and Y2O3:Eu3+ powders were obtained from the
decomposition of the precursors by solid-state microwave
heating at 500 °C for 20 min. Dai et al.236 prepared (Y,Gd)2O3
and (Y,Gd)2O3:Eu flower-like structures through two steps:
(Y,Gd)2(CO3)3·nH2O flower-like precursors were first synthe-
sized by the urea-based microwave-hydrothermal method, then
followed by heat treatment. The flower petals were composed
of nanoparticles with diameters of 50−100 nm.
Nanostructures of other metal oxides synthesized by
microwave heating have been less reported. For example, Al-
Hazmi et al.139 synthesized MgO nanowires with a diameter of
6 nm using Mg(CH3COO)2 and urea in aqueous solution by a
microwave-assisted hydrothermal process at 180 °C for 30 min,
followed by calcination at 600 °C for 1 h. Wang et al.140
prepared polymer-stabilized PdO nanoparticles through hydro-
lytic decomposition of H2PdCl4 in aqueous solution in the
presence of PVP and NaOH (or CH3COONa or sodium
benzoate) under microwave irradiation. Pan et al.141 prepared
PtO2 nanoparticles using H2PtCl6·6H2O, NaOH, CH3COONa,
and PVP in aqueous solution by the microwave and
conventional heating, respectively. PtO2 nanoparticles obtained
by microwave heating were smaller (1.68 nm) and more
narrowly distributed in size than those obtained by the
conventional heating (2.1 nm). PtO2 nanoparticles obtained
by microwave heating showed a higher catalytic activity than
those obtained by the conventional heating for hydrogenation
of cyclohexene. Qiu et al.237 prepared bundles of V2O5·xH2O
nanobelts with high flexibility from the microwave-assisted
refluxing reaction between VOSO4 and (NH4)2S2O8 in aqueous
solution at 100 °C for 1 h.
Siqueira et al.238 reported the microwave-assisted synthesis of
nanoparticles of NiWO4, CoWO4, and MnWO4 using the
corresponding metal nitrate and Na2WO4·2H2O in deionized
water at 110 or 150 °C for 10 or 20 min. Almeida et al.239
synthesized FeWO4 nanocrystals using an aqueous solution
containing (NH4)2Fe(SO4)2·6H2O and Na2WO4·2H2O by the
microwave-hydrothermal approach at 170 °C for 45 min.
BaWO4 nanoparticles were synthesized using BaCl2 and
Na2WO4·2H2O without any surfactant in aqueous solution
under microwave irradiation at 180 °C for 10 min.240 However,
BaWO4 nanosheets and nanobelts were obtained in the
presence of PVP under microwave irradiation at 100 °C for 5
min. It was found that the PVP concentration played an
important role in the formation of BaWO4 nanostructures with
different morphologies.241 Thongtem et al.242 prepared AWO4
(A = Ca, Sr) nanostructured materials with different
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morphologies such as spheres, peaches with notches, dumbbells
and bundles from metal salts, Na2WO4·2H2O, and CTAB in
aqueous solution under cyclic microwave irradiation at 300 W
for 10 min. AgIn(WO4)2 mesocrystals were prepared from an
aqueous solution containing AgNO3, In(NO3)3·4.5H2O, and
Na2WO4·2H2O by microwave heating at 180 °C for 20 min,
and the pH value played an important role in the phase
formation and shape evolution process. The oriented attach-
ment process was responsible for the formation of the
hierarchical structures.243 Sn2+-doped ZnWO4 nanocrystals
with sizes of ∼3.2−20.6 nm were prepared using ZnCl2,
SnCl2·2H2O, Na2WO4, and NaOH in aqueous solution (pH 7)
through the rapid microwave-assisted hydrothermal approach at
180 °C for 10 min.244
Bi2WO6 nanoplates were synthesized using Bi(NO3)3,
H2WO4, and ammonia as the starting reagents by the
microwave-hydrothermal approach.245 Bi2WO6 flower-like
nanostructures constructed by nanosheets with thicknesses of
∼15 nm were obtained using Bi(NO3)3·5H2O, Na2WO4,
HMTA, and HNO3 in aqueous solution via a rapid micro-
wave-assisted process at 180 °C for 5 min, the experiments
showed that HMTA and HNO3 played important roles in the
formation of flower-like nanostructures, and the Ostwald
ripening process was proposed for the formation of Bi2WO6
flower-like nanostructures.246 Flower-like aggregates of Bi2WO6
nanoflakes were obtained in acid precursor suspension by the
microwave-hydrothermal method, and the octahedral nano-
crystals of Bi3.84W0.16O6.24 were synthesized in the alkalescent
precursor system.247 NaY(WO4)2 hierarchical dumbbells
constructed by self-assembly of nanosheets were synthesized
using an aqueous solution containing Y(NO3)3·6H2O, triso-
dium citrate, and Na2WO4 by the microwave-assisted hydro-
thermal approach at 180 °C for 10 min, followed by heat
treatment at 600 °C in air for 1 h. It was found that the amount
of trisodium citrate played a crucial role in the self-assembly
process of the precursor.248
Lehnen et al.252 prepared Zn2SnO4 quantum dots with a
narrow size distribution using ZnCl2, SnCl4·5H2O, NaOH, and
SDS in aqueous solution under microwave-hydrothermal
conditions at 190 °C for different reaction times (5−60 min).
The experiments revealed a significantly shortened reaction
time in comparison with the conventional hydrothermal
synthesis. The stable aqueous suspension of Zn2SnO4 quantum
dots was further exploited for inkjet printing of functional
devices, which could be applied for humidity sensing. Zhang et
al.284 prepared Cd2Ge2O6 hierarchical nanostructures formed
by self-assembly of nanoneedles employing an aqueous solution
containing Cd(CH3COO)2·2H2O, GeO2, and N2H4·H2O via
the microwave-assisted approach at 180 °C for 10 min. It was
found that the reaction time, reaction temperature, volume of
N2H4·H2O, and cadmium source played important roles in the
formation of Cd2Ge2O6 hierarchical nanostructures. Sun et
al.253 synthesized ZnGa2O4 nanoparticles with an average
diameter of 10 nm from an aqueous solution containing
Ga(NO3)3·9H2O, ZnCl2, and ammonia via the microwave-
assisted hydrothermal method at 160 °C for 20 min.
Komarneni et al.256 reported the rapid microwave-hydro-
thermal synthesis of ∼5−20 nm ferrite nanoparticles such as
ZnFe2O4, NiFe2O4, MnFe2O4, and CoFe2O4 using nitrates of
zinc, nickel, manganese, cobalt, and iron at ∼164 °C for 4 min,
and their specific surface areas ranged from 72 to 247 m2 g−1.
Verma et al.255 synthesized MgFe2O4 nanoparticles with an
average particle size of ∼3 nm from an aqueous solution of
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Mg(NO3)2·6H2O, Fe(NO3)3·9H2O, and KOH under micro-
wave-hydrothermal conditions at 150 °C for 25 min. Nyutu et
al.257 preapred NiFe2O4 (6−20 nm) and ZnAl2O4 (∼9 nm)
nanoparticles by the continuous flow method that combined
microwave heating and in situ ultrasonic nozzle spray mixing;
the experimental results showed that the ultrasonic nozzle and
microwave irradiation complemented each other, with respect
to the purity of the products. Kim et al.258 prepared
Co1−xZnxFe2O4 and Ni1−xZnxFe2O4 nanoparticles with an
average particle size of ∼10 nm using FeCl3·6H2O, NiCl2·
6H2O, CoCl2·6H2O, and ZnCl2 in aqueous solution by the
microwave-hydrothermal method. Lai et al.259 prepared
Mn0.5Zn0.5Fe2O4 nanoparticles with an average size of about
10 nm by microwave-assisted coprecipitation at 100 °C, and it
was found that the particle size of the product increased with
microwave heating time.
BiFeO3 nanoparticles with sizes of 30−50 nm were prepared
using an aqueous solution containing Bi(NO3)3·5H2O, Fe-
(NO3)3·9H2O, HNO3, ammonia, and CTAB by microwave
heating at 100 °C for 20 min, followed by annealing at different
temperatures of 400−600 °C for 3 h in air.264 BiFeO3
nanostructures with spherical (15−55 nm) and rectangle-like
morphologies and Bi2Fe4O9 nanowires with a diameter of 40
nm were obtained using bismuth nitrate/iron nitrate alkaline
solutions under microwave-hydrothermal conditions.265 Perov-
skite-type BiFeO3 spherical nanocrystals with diameters of 10−
50 nm and sillenite-type Bi12Fe0.63O18.945 hexagonal-shaped
nanocrystals with sizes of 18−33 nm were synthesized using
Bi(NO 3 ) 3 ·5H 2 O, Fe(NO) 3 ·9H 2 O, KOH, and Na 2 CO 3
(Na2CO3 was not used for the synthesis of sillenite-type
Bi12Fe0.63O18.945) by the microwave-hydrothermal method at
180 °C for 1 h.266
Zawadzki et al.261 reported the microwave-assisted hydro-
thermal synthesis of ZnAl2O4 nanoparticles with a mean
particle size of 2.4 nm at 200 °C for 5 min. Conrad et al.
reported the microwave-assisted hydrothermal synthesis of Cu-
substituted ZnAl2O4 nanoparticles262 and Cu2+-containing
ZnGa2O4 solid solutions.254 In contrast, the analogous
conventional hydrothermal approach failed to generate phase-
pure products with homogeneously distributed morphologies,
indicating the advantages of the microwave-hydrothermal
synthesis over the conventional hydrothermal technique in
terms of shorter reaction time and homogeneous products.
Obata et al.263 prepared CoAl2O4 octahedral nanocrystals with
sizes of ∼70 nm by a microwave-hydrothermal process at 240
°C for 2 h, and inkjet printing with as-prepared aqueous
pigment ink was performed to decorate porcelain. The
nanoparticles were well dispersed in the aqueous suspension
with a high stability. The precursor concentration of the
suspension greatly affected the color tone of the resulting
particles, the printing system experienced no clogging, and the
printed image was of good quality.
Komarneni and Katsuki45,269 used commercial TiO2 as the
titanium source to prepare BaTiO3 nanoparticles with an
average particle size of ∼30 nm in an aqueous solution of
Ba(OH)2 by microwave heating at 90 or 180 °C. Jhung et al.270
prepared BaTiO3 nanoparticles with sizes less than 30 nm from
an aqueous solution containing TiCl4, BaCl2·2H2O, and KOH
by microwave heating at 180 °C for 30 min, and it was found
that the particle size decreased with increasing concentrations
of KOH and BaCl2. Similarly, Ti(OC4H9)4 was adopted as the
titanium source for the microwave-hydrothermal synthesis of
BaTiO3 nanoparticles with a nearly uniform size of 50 nm at
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150 °C for 50 min.271 Pazik et al.272 and Simões et al.273
reported the microwave-hydrothermal synthesis of
Ba 1−x Sr x TiO 3 (x = 0.1−0.4) nanoparticles using Ba-
(CH3COO)2, Ti(OC4H9)4 or TiCl4, Sr(NO3)2 or SrCl2·
6H2O, and NaOH in aqueous solution. Pazik et al.272 found
that the average particle sizes of the products were in the range
of 20−50 nm depending on the hydrothermal time (10−90
min). Nanoparticles (30−60 nm) of Eu3+-doped BaTiO3 were
obtained using Ba(CH3COO)2, titanium butoxide, Eu2O3 in
nitric acid, and NaOH in aqueous solution by the microwave-
hydrothermal method at 300 °C followed by calcination at
600−1000 °C for 1 h.274 Sulaeman et al.275 reported the
microwave-assisted hydrothermal synthesis of SrTiO3 nano-
particles with particle sizes of 30−40 nm and with various Sr/Ti
atomic ratios using SrCl2, Ti(OC3H7)4, and KOH in aqueous
solution. Moreira et al.276 conducted a detailed investigation of
microwave-assisted hydrothermal synthesis of SrTiO3 nano-
spheres to gain a better insight into thermodynamic, kinetic,
and reaction phenomena involved in SrTiO3 nucleation and
crystal growth processes. A possible formation mechanism was
proposed, based on dehydration of titanium and strontium
clusters followed by mesoscale transformation and self-
assembly by the oriented attachment mechanism, resulting in
a spherical-like shape. PbTiO3 nanowires with diameters of 20−
80 nm were synthesized using PbCl2, Ti(OC4H9)4, and KOH
as starting reactants by a microwave-hydrothermal process at
200 °C for 1.5 h.277
Nosheen et al.297 reported a phase transition from TiO2
particles to titanate nanotubes by the breakage of the Ti−O
bond. 1-D nanostructures of titanates (H2Ti4O9·nH2O) were
obtained using precursors of anatase and P-25 at a low
concentration of alkaline solution (1 M NaOH) by a
microwave-assisted soft chemical process at 100−110 °C for
12 h. Chou et al.279 synthesized Li4Ti5O12 microspheres
composed of nanoflakes as the building blocks by a
combination of the microwave-assisted hydrothermal method
and microwave post annealing. The synthesis was performed
using LiOH, H2O2, and titanium isopropoxide in aqueous
solution by microwave-assisted hydrothermal treatment at 150
°C for 15 min to yield the lithium titanium oxide precursor,
which was subsequently annealed by microwave heating in air
for 20 min to obtain Li4Ti5O12 microspheres. Zhang et al.280
prepared K2Ti6O13 nanowires with an average diameter of ∼10
nm and lengths ranging from hundreds of nanometers to tens
of micrometers using commercial TiO2 powder (anatase, ∼20
nm) and concentrated KOH aqueous solution under micro-
wave irradiation for 6 h at normal pressure.
BaMoO4 microspheres consisting of nanosheets were
synthesized through microwave reflux using BaCl2·2H2O,
(NH4)6Mo7O24·4H2O, and PVP in aqueous solution.281
CaMoO4 with a persimmon-like shape, which was made up
of nanosheets with thicknesses of 10−25 nm, was prepared
using Ca(NO3)2 and (NH4)6Mo7O24·4H2O in aqueous
solution by microwave heating for 1−15 min.282 γ-Bi2MoO6
nanoplates were synthesized using Bi(NO3)3·5H2O and
(NH4)2MoO4 in aqueous solution by the microwave-hydro-
thermal approach at 140 °C for 1 h.283
Shi et al.285 reported a fast microwave-assisted hydrothermal
process for the preparation of perovskite NaTaO3 nanocrystals
using Ta2O5 and NaOH as starting materials. The reaction
mixture was heated to 100−220 °C in 20 min and maintained
at the designated temperature for 5 min to 6 h. By pretreating
the Ta2O5 powder with ball milling, pure phase NaTaO3 could
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be synthesized under mild conditions through the formation of
an intermediate pyrochlore Na2Ta2O6 phase, while much
longer times were required in a conventional hydrothermal
process. That is, pretreatment of the raw material Ta2O5 by ball
milling is a crucial step in obtaining a pure perovskite NaTaO3
phase. The mechanism for the fast growth of pure NaTaO3
nanocrystals was proposed according to the phase evolution
during the reactions. An indirect formation route of Ta2O5 →
Na2Ta2O6 → NaTaO3 was suggested when using the ball
milled Ta2O5 as the starting material, while a direct conversion
from Ta2O5 to NaTaO3 was put forward for the reaction
starting from Ta2O5 without ball milling. They proposed that
the indirect path is a process with a lower thermodynamic
energy barrier in comparison with the direct one, so that it can
drive a complete reaction to produce the pure perovskite
NaTaO3 under mild conditions. SnNb2O6 nanosheets with
thicknesses of 1−4 nm were prepared using Nb2O5·nH2O (n =
5−8) and SnCl2 in aqueous solution by the microwave-assisted
hydrothermal method without exfoliation at 200 °C for various
times.286
BiVO4 nanostructures with the tetragonal and monoclinic
phases were prepared from aqueous solutions containing
Bi(NO3)3 and NaVO3 by the rapid microwave-assisted method,
and the highly crystalline phase converted irreversibly from
tetragonal to monoclinic BiVO4 with prolonged microwave
irradiation time.287 BiVO4 hollow microspheres constructed by
nanorods were synthesized using an aqueous solution
containing Bi(NO3)3·5H2O and NH4VO3 in the presence of
ethylenediaminetetraacetic acid (EDTA) by the microwave-
hydrothermal method at 180 °C for 3 h, and it was found that
the amount of EDTA played a crucial role in determining the
morphology of the product.288 CeVO4 nanoparticles were
synthesized using Ce(NO3)3 and NaVO3 under microwave
irradiation for 10 min, and the sizes of CeVO4 nanoparticles
were in the range of 6−18 nm and were dependent on the pH
value.289 YVO4 nanoparticles were obtained by a similar
method.290 LaVO4:Ln3+ (Ln3+ = Eu3+, Tb3+, Sm3+, and Dy3+)
nanorods with diameters of 10−20 nm and lengths up to 200
nm were prepared using Tb(NO3)3, La(NO3)2, and NH4VO3
in aqueous solution (pH between 8 and 9) by simultaneous
supersonic and microwave irradiation at a low temperature (70
°C) for 45 min, and red, green, orange-red, and blue-yellow
emission colors were obtained using different lanthanide
ions.291
2.3. Metal Sulfides
Nanostructured metal sulfides are important functional
materials and widely used in many areas. Microwave-assisted
rapid synthesis of metal sulfide nanostructures has aroused
much interest due to its advantages especially in terms of very
short processing time. In the microwave-assisted synthesis of
metal sulfide nanostructures in aqueous solution, a water-
soluble metal salt is usually used as the metal source, a sulfur
source is used to provide S2− ions, and an additive or surfactant
is sometimes adopted to control the morphology and size of
the product. A variety of metal sulfide nanostructures with
various morphologies have been reported by the rapid
microwave-assisted method in aqueous solution, including
PbS,298−300 CuS,301 Cu9S8,302 CdS,303−309 ZnS,303,310−313
Ag 2 S, 314 Bi 2 S 3 , 315,316 HgS, 317 AgInS 2 , 318 AgIn 5 S 8 , 319
CuInS2,320 CuInSe2,320 CdIn2S4,321 and Cu2ZnSnS4.322 The
sulfur sources commonly adopted in microwave-assisted
synthesis of metal sulfide nanostructures in aqueous solution
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include Na2S,305,307,311,317 CS2,304 Na2S2O3,309
NH2CSNH2,298,301,308,316,321 NH2NHCSNH2,299
CH3CSNH2,302,303,306,310,312,314,318,319,322 and 3-mercaptopro-
panoic acid.300
A micelle-assisted solution route was adopted to synthesize
pure and Zn-doped PbS nanocrystals using PbCl2ZnCl2, 3-
mercaptopropanoic acid, thioacetamide, and NaOH under
microwave irradiation for 40 s, and the micelle structure played
an important role in the formation of PbS nanocrystals.300 PbS
nanostructures with different sizes and morphologies were
prepared using Pb(CH3COO)2·3H2O and thiourea in the
solvent of distilled water, ethanol, ethylene glycol, or PEG-200
by microwave heating.298 Nanoparticle-assembled PbS nano-
tubes with diameters of 20−40 nm were prepared from an
aqueous solution containing Pb(NO3)2, NH2NHCSNH2, and
NaOH through a microwave-assisted route without using any
surfactant.299 Bi2S3 nanorods with diameters of ∼10 nm were
prepared from a formaldehyde aqueous solution containing
Bi(NO3)3·5H2O and thiourea under microwave irradiation.315
Bi2S3 nanorods in flower-shaped bundles were synthesized
using thiourea as the sulfur source and PVP as a surfactant by a
microwave-assisted hydrothermal process at 200 °C for 1 h.316
Cu9S8 nanorods with diameters of 5−10 nm and lengths of
30−60 nm were prepared from an aqueous solution containing
Cu(NO3)2·3H2O, thioacetamide, and SDS under pulsed
microwave irradiation for 20 min.302 CuS hierarchical flower-
like spheres and self-assembled chains were synthesized using
CuCl2·2H2O, thiourea, NaOH, and EDTA in aqueous solution
under pulsed microwave irradiation for 20 min. The as-
prepared CuS flower-like spheres were constructed by nano-
sheets as primary building units, whereas the hierarchical chains
were formed by the oriented attachment of the flower-like
spheres.301
ZnS and CdS nanoparticles were prepared by a fast
microwave-assisted reaction between CdCl2 or Zn(CH3COO)2
and thioacetamide in aqueous solution, and the particle size was
∼9 and 3 nm for CdS and ZnS, respectively.303 ZnS
nanoparticles (∼6.5 nm) and doped ZnS nanoparticles were
synthesized using corresponding metal salts and Na2S via
microwave irradiation for 10 min, and it was found that the
luminescent properties of ZnS nanoparticles were greatly
affected by either the microwave irradiation time or the
dopants of various metallic ions (Ag+, Cu2+, Ce3+, and Sn4+).311
ZnS nanoballs formed by self-assembly with nanoparticles were
prepared using Zn(CH3COO)2 and thioacetamide in aqueous
solution via a microwave-assisted route, and ZnSO4 and
Zn(NO3)2 were also used as the zinc source to prepare ZnS
nanoparticles instead of nanoballs.310 Mehta et al.312 prepared
monodisperse PEG-coated ZnS nanoparticles with a cubic zinc
blend structure and diameters of ∼11 ± 3 nm using
Zn(CH3COO)2·2H2O, CH3CSNH2, and PEG in aqueous
solution by microwave heating (Figure 9). It can be seen
from the TEM micrographs in Figure 9 that a thin layer of PEG
was uniformly coated on the surface of the as-synthesized ZnS
nanoparticles. The fast microwave heating accelerated the
decomposition of thioacetamide to provide S2− ions:312
CH3CSNH 2 + H 2O → CH3CONH 2 + H 2S
H 2S → 2H+ + S2 −
The nucleation of ZnS occurred due to the reaction between
Zn2+ and S2− ions:
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Figure 9. Typical TEM micrographs of PEG-coated ZnS nanoparticles
prepared by a microwave-assisted process. Reproduced with
permission from ref 312. Copyright 2011 Elsevier B.V.
Zn 2 + + S2 − → ZnS
A similar method was reported for the preparation of
Zn 1−x Cd x S particles using Zn(CH 3 COO) 2 ·2H 2 O, Cd-
(CH3COO)2·2H2O, and CH3CSNH2 in aqueous solution by
household microwave oven heating for 6 min,313 in which no
PEG was used as a surfactant, and the sizes of Zn1−xCdxS
particles were much larger (100−300 nm) than those
synthesized using PEG (∼11 nm).312
CdS nanoparticles were produced from the reactions
between CdCl2 and various sulfur sources in aqueous
suspension of laponite, which was used for good dispersion
of CdS nanoparticles and for facilitating the formation of the
product by providing a basic environment when CS2 was used
as a sulfur source; CdS structures with different shapes and
sizes were obtained by adjusting reaction conditions.304 CdS
hollow nanospheres packed with square subunits were
fabricated using CdSO4·(8/3)H2O, Na2S·6H2O, and pentaer-
ythritol in aqueous solution via microwave irradiation in a
rectangular waveguide at room temperature (25 °C).305 CdS
nanowires on DNA scaffolds were synthesized using Cd-
(ClO4)2, thioacetamide, and DNA in aqueous solution under
pulsed microwave irradiation for 1 min. Highly selective
deposition on DNA was obtained by specific complexation
between Cd2+ ions and DNA molecules, followed by
decomposition of thioacetamide to S2− to form CdS. This
one-step process did not perturb the overall conformation of
the DNA chain.306 CdS nanotubes were synthesized using
CdSO4 and Na2S in aqueous solution via microwave irradiation,
the solutions were maintained in a circular waveguide at room
temperature (25 °C) and under ambient pressure for 20 days,
and the waveguide was made of copper with a diameter of 95
mm in cross-section, which propagated 10 W of microwave
irradiation (2.45 GHz).307 Arrays of noncrystalline CdS
nanotubes were prepared by employing an aqueous solution
containing CdCl2 and thiourea in the presence of anodic
porous alumina membrane under microwave refluxing for 10
min.308 Hu et al.309 demonstrated a two-step microwave-
assisted coating of CdS nanoparticles on the surface of carbon
spheres. First, cadmium ions were adsorbed on the hydrophilic
shell of carbon spheres. Second, the above carbon spheres were
dispersed in distilled water, and then Na2S2O3·5H2O as the
sulfur source was added. The mixture was heated under
microwave refluxing at 280 W for different times, resulting in
C@CdS hybrid spheres. The thickness of the CdS nanoparticle
shell could be varied by the microwave heating time. In
addition, CdS nanospheres were prepared using CdCl2·2.5H2O,
Na2S2O3·5H2O, and PVP in aqueous solution via microwave
refluxing at 28 W for different times.
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Ag2S nanoworms with diameters of ∼50 nm were prepared
by reacting AgNO3 with thioacetamide in the presence of BSA
in aqueous solution via the rapid microwave-assisted hydro-
thermal method. The as-prepared Ag2S nanoworms were
formed by assembly of Ag2S nanoparticles and stabilized by a
layer of BSA.314 HgS nanotubes were prepared using HgCl2
and Na2S in aqueous solution by microwave heating under
ambient conditions, and the reaction solution was maintained
in a circular waveguide at room temperature (25 °C) and under
ambient pressure for 20 days. The waveguide was made of
copper with a diameter of 95 mm in cross section, which
propagated 10 W microwaves (2.45 GHz).317
AgInS2 and AgIn5S8 nanoparticles were synthesized using
thioacetamide as the sulfur source by the microwave-hydro-
thermal method.318,319 Bensebaa et al.320 reported the micro-
wave-assisted preparation of CuInS2 and CuInSe2 nanoparticles
using Cu, In, and S/Se precursors in the presence of mercapto-
acetic acid in aqueous solution for 30 min. Apte et al.321
synthesized CdIn2S4 hierarchical nanostructures using Cd-
(NO3)2·4H2O, In2(NO3)2, and thiourea by microwave-assisted
reactions, and different capping agents such as Titron X, SDS,
and sodium lauryl sulfate were also used. Shin et al.322
synthesized Cu2ZnSnS4 nanocrystals by a two-step process. In
the first step, the precursor powder was obtained from an
aqueous solution containing Cu(CH3COO)2, Zn(CH3COO)2,
SnCl2, and thioacetamide under microwave irradiation at 700
W for 10 min. In the second step, the precursor powder was
sulfurized by annealing in H2S (5%)/N2 (95%) at 550 °C for 1
h in a commercial furnace.
2.4. Metal Selenides
As compared to the microwave-assisted synthesis of nano-
structured metal oxides and sulfides, the microwave-assisted
synthesis of metal selenide nanostructures has been less
reported, possibly due to relatively high-cost, less available
selenide sources and challenges in the preparation. The
rapidness of microwave-assisted synthesis is more remarkable
for nanostructures of metal selenides, with significantly reduced
reaction time to minutes. Zhu et al.323 synthesized nano-
particles of CdSe, PbSe, and Cu2−xSe by fast microwave
refluxing reactions between acetates or sulfates of Cd, Pb, Cu,
and Na2SeSO3 in the presence of the complexing agent in
aqueous solution. It was found that the crystal phase of CdSe
was dependent on microwave reaction time. CdSe with a cubic
structure was obtained by microwave heating for 10 min;
however, longer reaction time led to a crystal phase transition.
When the reaction time was prolonged to 30 min, CdSe with a
hexagonal structure was obtained. Gallagher et al.324 reported
the microwave-assisted synthesis of chiral CdSe quantum dots
by using chiral stabilizers dextrorotatory (D-) and levorotatory
(L-) enantiomers as well as the racemate (rac-) of the amino
acid in aqueous solution at 1500 W for 40 s. CdSe quantum
dots were prepared in aqueous solution under microwave-
assisted hydrothermal conditions at temperatures between
120−210 °C for minutes.325 CdSe nanoparticles with a cubic
phase and narrow photoluminescent emission were synthesized
in aqueous solution in the presence of citric acid under
microwave irradiation.326
ZnSe nanocrystals were synthesized using ZnCl2 and NaHSe
in the presence of 3-mercaptopropionic acid as a stabilizer in
aqueous solution (pH 6.5) by microwave heating at 140 °C.327
Glutathione-capped ZnSe quantum dots with sizes of 2−3 nm
were prepared using Na2SeO3 as a selenium source to replace
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commonly adopted NaHSe or H2Se in aqueous solution by
microwave refluxing under air atmosphere for 1 h. In this
method, Na2SeO3 was reduced by NaBH4 under ambient
conditions to generate Se2− ions.328 ZnSe:Cu and ZnSe:Mn
quantum dots with a passivated surface were synthesized using
Zn(NO3)2·6H2O, CuCl2·2H2O or MnCl2·4H2O, NaHSe, 3-
mercaptopropionic acid, and NaOH in aqueous solution by
microwave refluxing two times for a total heating time of 20
min.329
Bensebaa et al.320 prepared CuInSe2 nanoparticles in an
aqueous solution containing Cu, In, and S/Se precursors in the
presence of mercapto-acetic acid by microwave heating for 30
min. A green microwave synthetic route to CuIn1−xGaxSe2
nanoparticles with x = 0, 0.25, and 0.5 and with sizes of several
nanometers in aqueous solution at 95 °C for 30 min was
described by Al Juhaiman et al.330 In this method, appropriate
amounts of Cu(CH3COO)2·2H2O, InCl3, GaCl3, Na2Se, and
mercapto-acetic acid were used as the starting reagents. The as-
prepared nanoparticles were stable in aqueous solution for
several weeks.
2.5. Metal Tellurides
The preparation of nanostructured metal tellurides is even
more challenging as compared to the synthesis of metal
selenides. The reported work has focused on the microwave-
assisted synthesis of CdTe nanostructures, which is a very
important semiconductor and has wide applications in various
fields. CdTe is used as an infrared optical window and a solar
cell material. It is usually sandwiched with CdS to form a p−n
junction photovoltaic solar cell.
The traditional aqueous solution route to the preparation of
CdTe nanocrystals is usually time-consuming. NaHTe has been
commonly used as the tellurium source. Li et al.331 reported the
microwave-assisted synthesis of high-quality CdTe nanocrystals
using CdCl2, NaHTe, 3-mercaptopropionic acid, and NaOH in
aqueous solution. At a relatively low temperature (below or
equal to 160 °C), CdTe nanocrystals with various sizes and
with high quantum yield were synthesized by simply varying the
reaction temperature and reaction time. This method allows the
rapid preparation of a series of CdTe nanocrystals emitting at
the green to near-infrared spectral window (505−733 nm) at
moderate temperatures. Similarly, highly luminescent CdTe
nanocrystals with diameters of ∼2−4 nm were rapidly prepared
(1−30 min) using CdCl2 and NaHTe in the presence of 3-
mercaptopropionic acid in aqueous solution through micro-
wave irradiation.332 CdTe nanocrystals were prepared using
CdCl2 and NaHTe at pH 11.4 in the presence of thioglycolic
acid in aqueous solution by microwave heating at 90 °C for 15
min. When 3-mercaptopropionic acid was substituted for
thioglycolic acid, the pH value of precursors was adjusted to
8.4, and the reaction temperature was raised to 100 °C.333 Guo
et al.334 synthesized N-acetyl-L-cysteine-capped CdTe nano-
crystals with the average particle sizes ranging from 2.5 to 3.6
nm using CdCl2 and NaHTe in the presence of N-acetyl-L-
cysteine via microwave heating at 95 °C. A series of CdTe
samples were prepared by controlling the microwave heating
time. Fluorescent CdTe quantum nanospheres with sizes of
∼35 nm consisting of quantum dots were synthesized using
NaHTe as the tellurium source in the presence of poly-
(allylamine) in aqueous solution under microwave irradiation at
100 °C for 15 min. He et al.335 prepared multicolor CdTe
nanospheres with maximum emission wavelengths ranging
from 525 to 610 nm; they found that only irregularly shaped
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quantum dots−polymer complexes were obtained when the
conventional heating was used, indicating the important role of
microwave heating in the formation of CdTe nanospheres.
Na2TeO3 has also been adopted as a tellurium source. A one-
pot microwave-assisted reduction route was reported for the
synthesis of highly luminescent CdTe quantum dots using
Na2TeO3 as the tellurium source in an aqueous environment. It
was found that the experimental parameters including the
reaction temperature and time, pH value of solution, and molar
ratio of 3-mercaptopropionic acid to Cd2+ had considerable
effects on the particle size and photoluminescence quantum
yield of CdTe quantum dots. 336 Glutathione-capped
Zn1−xCdxTe quantum dots were obtained using CdCl2·
2.5H2O, ZnCl2, Na2TeO3, KBH4, and glutathione under
microwave refluxing.337 CdSexTe1−x (0 ≤ x ≤ 1) nanocrystals
were synthesized by coreduction of Na2SeO3 and Na2TeO3 in
aqueous solution under microwave irradiation at 120 °C for
10−30 min.338
2.6. Inorganic Biomaterials − Hydroxyapatite and Calcium
Phosphates
Hydroxyapatite (HAP) and calcium phosphates are important
inorganic biomaterials and have wide applications in the
biomedical fields. In recent years, the microwave-assisted
synthesis of nanostructured biomaterials has aroused much
interest. Lee et al.339 prepared HAP and biphasic tricalcium
phosphate nanopowders using Ca(OH)2 as the calcium source,
H3PO4 as the phosphorus source, and ammonia in aqueous
solution by microwave heating at 700 W for 25 min. Finally, the
calcination was carried out at 750 °C in air. The synthesized
powders consisted of spherical nanoparticles with the average
sizes in the range of 50−90 nm. In the pH range of 6−12, two
phases of HAP and β-tricalcium phosphate coexisted. The
average particle size of the synthesized powders decreased as
the pH of the solution increased, and the particle sizes at pH 6
and 12 were about 80−90 and 50−70 nm, respectively. The
yield of HAP increased as the pH value of solution increased,
while the yields of α-tricalcium phosphate and β-tricalcium
phosphate decreased. At pH 12, HAP nanoparticles were
obtained.
Vani et al.340 prepared mesoporous HAP nanorods with
lengths of 40−75 nm and a diameter of 25 nm using a solution
(pH 10) containing Ca(NO3)2·4H2O, (NH4)2HPO4, and
ammonia under microwave irradiation at 900 W for 30 min.
Lak et al.341 obtained single-crystalline HAP nanorods with
diameters of ∼25 nm and lengths of ∼100 nm using Ca(NO3)2·
4H2O, Na2HPO4, NaOH, and EDTA under microwave
irradiation at 900 W for 2.5 min. The microwave-assisted
reactions with the same reactants for 30 min produced HAP
nanorods, and bow-knot-like and flower-like nanostructures. It
was found that the pH value and the complex reagent EDTA
played important roles in the formation of HAP nanostruc-
tures.342
The combination of sonochemistry and microwave irradi-
ation provides a new unique route for the preparation of
inorganic nanostructures in liquid phase. Liang et al.343
reported the template-free sonochemistry-assisted microwave
method for the synthesis of mesoporous HAP nanostructures
using Ca(NO3)2·4H2O and (NH4)2HPO4 in aqueous solution
(pH 10.5) for 10 min. The product consisted of HAP nanorods
with lengths of 50−100 nm and widths of about 20 nm. N2
adsorption−desorption isotherms revealed an irregular meso-
porous structure. It was found that microwave radiation played
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a dominant role in the formation of mesoporous structure,
while ultrasound irradiation acted as a supporting role.
Chen et al.344 reported the microwave-assisted hydrothermal
synthesis of multifunctional Eu3+/Gd3+ dual-doped HAP
nanorods using CaCl2, Na2HPO4·12H2O, europium nitrate,
gadolinium nitrate, NaOH, and polylactide-block-
monomethoxy(poly(ethylene glycol)) (PLA-mPEG) in deion-
ized water at 200 °C. Figure 10 shows both undoped and
Figure 10. (a−d) TEM micrographs of the samples prepared by the
microwave-assisted hydrothermal method at 200 °C for 30 min: (a)
undoped HAP nanorods; (b−d) Eu3+/Gd3+-HAP nanorods (Eu3+/
Gd3+ molar ratio = 1:1). (e,f) Length distributions of HAP nanorods
measured from TEM micrographs: (e) undoped HAp nanorods; (f)
Eu3+/Gd3+-HAP nanorods. Reproduced with permission from ref 344.
Copyright 2011 Elsevier Ltd.
doped HAP samples consisted of nanorods with diameters in
the range of 10−50 nm. Figure 10d shows a high-resolution
TEM (HRTEM) image of a single Eu3+/Gd3+-HAP nanorod;
the fringe spacings measured in the HRTEM image were 0.46
and 0.34 nm, corresponding to the crystal planes of (110) and
(002), respectively. The preferential growth direction of the
nanorod was along the [001] direction of hexagonal HAP. As
compared to undoped HAP nanorods, the sizes of Eu3+/Gd3+-
HAP nanorods became smaller. The average lengths of
undoped HAP and Eu3+/Gd3+-HAP nanorods were measured
to be 265.4 ± 143.5 and 53.0 ± 18.2 nm, respectively. The
doping of Eu3+ and Gd3+ led to smaller size and narrower size
distribution of nanorods (Figure 10e and f). The photo-
luminescence, drug delivery, and in vivo imaging of the
products were also investigated. The photoluminescent and
magnetic multifunctions of HAP nanorods were realized by the
dual-doping with Eu3+ and Gd3+. The as-prepared Eu3+/Gd3+
dual-doped HAP nanorods exhibited little toxicity to the cells in
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vitro, a high drug adsorption capacity, and sustained drug
release, and they are promising for bioimaging applications.
Han et al.345 synthesized HAP nanostructures using H3PO4
and Ca(OH)2 as starting reagents by the microwave-hydro-
thermal method. HAP nanostructures consisted of needles with
widths of ∼4−15 nm and lengths of 20−50 nm and spherical
nanoparticles with diameters of ∼10−30 nm. The applied
microwave power and molar ratio of Ca/P had significant
effects on the product. Meejoo et al.346 reported rapid synthesis
of HAP needle-shaped nanocrystals with a diameter of ∼50 nm
and length of 200 nm using Ca(OH)2 and (NH4)2HPO4 in
aqueous solution by microwave heating at 850 W for 20 min.
Siddharthan et al.347 obtained calcium-deficient HAP nano-
needles with lengths of 16−39 nm and widths of 7−16 nm and
with a Ca/P ratio of 1.5 using Ca(NO3)2·4H2O, H3PO4, and
ammonia under microwave irradiation in a household micro-
wave oven for 15 min.
The surfactant-free rapid microwave-assisted hydrothermal
synthesis of HAP nanosheet-assembled flower-like hierarchical
nanostructures was reported using an aqueous solution
containing Ca(CH3COO)2·H2O and NaH2PO4·2H2O (pH
4.5) at 100 °C for 5 min.348 The morphology of the product
was dependent on the experimental conditions such as the
microwave heating temperature and heating time. HAP flower-
like hierarchical nanostructures were obtained at a lower
temperature (100 °C), and polyhedra were obtained at a higher
temperature (200 °C). The loading capacities of the as-
prepared HAP flower-like hierarchical nanostructures for BSA,
hemoglobin, and fish sperm DNA were determined to be 165,
164, and 112 mg g−1, respectively. The protein release was
conducted at different pH values (pH 7.2, 5.5, and 4.8) in
phosphate buffered saline, and the pH-sensitive protein release
behavior was found.348
Wang et al.349 reported a rapid microwave-assisted hydro-
thermal route to flower-like nanostructured HAP hollow
microspheres assembled with nanosheets with a hierarchical
morphology using Ca(CH3COO)2, NaH2PO4, and Na2HPO4
at 120 °C for 5 min. The presence and concentration of block
copolymer PLA−PEG played an important role in the
formation of HAP hollow microspheres. The possible
formation mechanism of HAP hollow microspheres was
proposed. The as-prepared HAP hollow microspheres were
explored as the anticancer drug (mitoxantrone (MIT)) carriers
for cellular delivery. The MIT-loaded HAP hollow micro-
spheres exhibited a sustained drug release behavior in vitro. The
MIT intracellular accumulation was observed in both MIT-
sensitive human breast cancer (MCF-7) cells and MIT-resistant
human breast cancer (MCF-7/MIT) cells for MIT-loaded HAP
hollow microspheres, suggesting that the MIT could be
successfully delivered into the MCF-7 and MCF-7/MIT cells
with the help of nanocarriers. They also demonstrated the
template-free microwave-assisted hydrothermal synthesis of
HAP hollow microspheres constructed by the self-assembly of
nanosheets using Ca(CH3COO)2, Na2HPO4, NaH2PO4, and
sodium citrate in aqueous solution. The effects of experimental
parameters on the product were investigated, and a possible
formation mechanism was proposed. The HAP hollow
microspheres exhibited 3-D nanoporous network structure.
The use of cheap reagents, relatively low and flexible
temperature (80−140 °C), and short reaction time (30 min)
makes this approach rapid and economical.350
Escudero et al.351 reported the microwave-assisted hydro-
thermal synthesis of europium-doped HAP and fluoroapatite
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nanostructures functionalized with poly(acrylic acid) from
aqueous basic solutions containing Ca(NO3)2·4H2O, Eu-
(NO3)3·5H2O, NaH2PO4, and poly(acrylic acid) as well as
NaF in the case of the fluoroapatite at 180 °C for 1 h with a
heating rate of 14 °C min−1. In both cases, a spindle-like
morphology was obtained, resulting from an aggregation
process of smaller subunits, as shown in Figure 11. The sizes
Figure 11. (A) TEM micrograph of Eu-doped HAP spindle-like
nanostructures functionalized with poly(acrylic acid). (B) HRTEM
image of a single spindle-like nanostructure in which several planes
compatible with the HAP structure, as well as the d spacings, are
shown. Reproduced with permission from ref 351. Copyright 2013
American Chemical Society.
of the spindles were 191 × 40 nm for HAP and 152 × 38 nm
for fluoroapatite. The as-prepared samples showed negligible
toxicity for Vero cells and high colloidal stability (up to at least
1 week) in 2-(N-morpholino)ethanesulfonic acid at pH 6.5,
which is a commonly used buffer for physiological pH. All of
these features make both kinds of apatite-based nanostructures
promising for biomedical applications.
Carbonated HAP nanostructures were synthesized using an
aqueous solution containing Ca(NO3)2, (NH4)2HPO4, and
ammonia (pH 10.8) via an ultrasound-assisted microwave
irradiation process. Rod-like nanocrystals with diameters of ∼8
nm and lengths of ∼30 nm were obtained at a high yield of
98.8% in a short period of time (5 min). In addition, the
crystallization process was promoted with the increase of
ultrasonic and microwave power and irradiation time.352
Rameshbabu et al.353 prepared Ag (0.5−3 at. %) substituted
needle-like HAP (AgHAP) nanostructures with lengths of 60−
70 nm and widths of 15−20 nm using Ca(OH)2, AgNO3, and
(NH4)2HPO4 by microwave heating for 30 min. The
antibacterial effect of AgHAP against Escherichia coli and
Staphylococcus aureus was observed even for a low concen-
tration of Ag+ ions (0.5%). André et al.354 adopted the
microwave-hydrothermal method to prepare Eu-doped HAP
nanorods with diameters from 9 to 26 nm using an aqueous
solution containing Ca(NO3)2·4H2O, Eu2O3, (NH4)3PO4, and
HNO3 at 140 °C for different times (1, 20, or 40 min).
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Very recently, exciting progress has been made by Zhu’s
research group in the use of biocompatible phosphorus-
containing biomolecules as organic phosphorus sources for
the microwave-assisted environmentally friendly synthesis of
nanostructured calcium phosphates and HAP.355−360 Inorganic
phosphate ions have mostly been used as the phosphorus
source in the synthesis of calcium phosphate nanostructures.
However, in the case of supersaturation of Ca2+ ions and PO43−
ions in the precursor solution, rapid nucleation and a
disordered growth of calcium phosphates may occur, and the
morphology and size of the products are difficult to control. As
compared to the inorganic phosphorus sources, the use of
phosphorus-containing biomolecules as organic phosphorus
sources has several advantages.359 First, the phosphorus source
exists in the form of phosphate groups in an organic
biomolecule and no PO43− ions exist in the precursor solution,
thereby avoiding the fast nucleation and disordered growth of
the calcium phosphates. Second, organic biomolecules generally
require certain conditions such as heating in aqueous solution
to hydrolyze to form PO43− ions. The hydrolysis conditions can
be used to control the hydrolysis rate of organic biomolecules,
which determines the morphology, size, and structure of the
calcium phosphate product. Third, organic biomolecules
hydrolyze to form PO43− ions in a progressive manner, thereby
avoiding the fast nucleation and disordered growth of calcium
phosphates. Fourth, organic biomolecules can regulate the
crystal growth of calcium phosphates, for example, by
stabilizing the initially formed amorphous calcium phosphate
(ACP) phase in aqueous solution and inhibiting the trans-
formation of ACP into HAP. Fifth, biomolecules are
biocompatible and exist in vivo. Thus, they are essentially
nontoxic with high biocompatibility. On the basis of these
points, biocompatible phosphorus-containing biomolecules as
organic phosphorus sources are considered to be very
promising for the “green” synthesis of calcium phosphate
nanostructures. The reported organic phosphorus sources
adopted for microwave-assisted synthesis of nanostructured
calcium phosphates and HAP include adenosine 5′-triphos-
phate (ATP), fructose 1,6-bisphosphate, creatine phosphate,
and pyridoxal-5′-phosphate.355−360
Adenosine 5′-triphosphate (ATP) is the most common cell’s
energy carrier in the biological systems. It can be used as a
promising biocompatible organic phosphorus source for the
rapid synthesis of nanostructured calcium phosphates and HAP
by microwave heating.355,356,360 Qi et al.355 reported the
microwave-assisted hydrothermal synthesis of HAP nanowires
using CaCl2·2H2O and ATP in aqueous solution without any
surfactant. HAP nanowires with diameters of ∼30 nm could be
obtained by this rapid method at 160 °C for a short period of
time (30 min). The effects of the reaction temperature and time
on the morphology of the product were investigated. This
method does not need any hard template or surfactant,
avoiding the procedures and cost for their removal in the
product. The advantages of this method are simple, rapid,
surfactant-free, and environment-friendly. Another work has
been reported on the synthesis of highly stable ACP porous
nanospheres with a relatively uniform size and an average pore
diameter of ∼10 nm by using CaCl2·2H2O as the calcium
source and ATP as both the phosphorus source and the
stabilizer in the microwave-assisted hydrothermal process at
120 °C for 10 min (Figure 12).356 In this method, ATP
biomolecules are used as the organic phosphorus source for the
formation of ACP porous nanospheres with a relatively uniform
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Figure 12. SEM image of ACP porous nanospheres synthesized by
using CaCl2·2H2O as the calcium source and ATP as both the
phosphorus source and the stabilizer by the microwave-assisted
hydrothermal method at 120 °C for 10 min. Reproduced with
permission from ref 356. Copyright 2012 Wiley-VCH.
morphology and size, and the residual ATP molecules can be
used as the stabilizer for ACP porous nanospheres, leading to
high stability of ACP porous nanospheres in aqueous solution.
The as-prepared ACP porous nanospheres were efficient as the
drug nanocarrier for anticancer drug loading and sustained drug
release. The ACP porous nanosphere drug-delivery system
exhibited a high ability to damage tumor cells after loading
docetaxel, and thus is promising for the application in
anticancer treatment.356 The experimental results show that
by adjusting the experimental parameters (temperature and
time), the crystal phase and morphology of the product can be
controlled.
Zinc-doped amorphous calcium phosphate (Zn/ACP)
mesoporous microspheres were prepared using CaCl2, ZnCl2,
and ATP as a biocompatible organic phosphorus source by the
microwave-assisted hydrothermal method at 110 °C for 10 min.
It was found that ATP was the main factor for stabilizing ACP
in aqueous solution and Zn2+ ions were doped in ACP for the
antibacterial benefit. The experimental results revealed that
some residual ATP molecules were adsorbed on the surface of
the Zn/ACP mesoporous microspheres. The Zn/ACP
mesosporous microspheres exhibited pH-sensitive Zn2+ ion
release behavior and good antibacterial activity against bacteria
Staphylococcus aureus and Escherichia coli, indicating they are
promising for the applications in the biomedical fields.360
Fructose 1,6-bisphosphate trisodium salt (FBP) has also been
used as a biocompatible organic phosphorus source for rapid
synthesis of a variety of calcium phosphate nanostructures,
including porous ACP microspheres, HAP nanorods, and
ACP/HAP composite microspheres, by the rapid microwave-
assisted hydrothermal method.357 The important role of FBP
and the effect of the experimental conditions on the formation
and evolution of calcium phosphate nanostructures were
investigated. This method combines the advantages of FBP as
an organic phosphorus source with rapid microwave volumetric
heating; it is facile, rapid, surfactant-free, and environmentally
friendly. Moreover, the as-prepared porous ACP microspheres
exhibited a relatively high drug loading capacity and good
sustained drug release behavior; thus, they are promising for the
application in drug delivery.357
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Qi et al.358 reported the rapid and environmentally friendly
synthesis of HAP hierarchically nanostructured porous hollow
microspheres by the microwave-assisted hydrothermal method
at 120 °C for 10 min. In this method, biocompatible
phosphorus-containing creatine phosphate is used as an organic
phosphorus source instead of the inorganic phosphorus source
that is typically employed in the literature. Creatine phosphate
is a biomolecule that provides energy to cells by synthesizing
ATP. This method combines the advantages of creatine
phosphate as an organic phosphorus source with rapid
microwave volumetric heating for the controlled synthesis of
HAP nanostructured materials. The as-prepared product
consisted of HAP nanosheets/nanorods as the building blocks
with a nanoporous structure with an average pore size of ∼20.6
nm. The important role of creatine phosphate and the influence
of the experimental conditions on the morphology and size of
the product were systematically investigated. The as-prepared
HAP product was explored for potential applications in drug
delivery and protein adsorption and release, which exhibited a
relatively high drug loading capacity and high protein
adsorption ability, by using ibuprofen as a model drug and
hemoglobin as a model protein.
Zhao et al.359 reported the biomolecule-assisted microwave-
hydrothermal rapid synthesis of HAP hierarchical nanostruc-
tures with different morphologies by using pyridoxal-5′-
phosphate as a new biocompatible organic phosphorus source,
and various HAP hierarchical nanostructures have been
obtained including HAP nanorod-assembled hierarchical
hollow microspheres, HAP nanorod-assembled hierarchical
microspheres, and HAP nanosheet-assembled hierarchical
microspheres. This preparation method is time-saving, with
the microwave heating time as short as 5 min. The effects of the
experimental conditions on the morphology and crystal phase
of the product were investigated, and a possible formation
mechanism was proposed. The products were explored for
potential applications in protein adsorption and drug delivery.
The experimental results showed that the HAP nanorod-
assembled hierarchical hollow microspheres had a high drug/
protein loading capacity and sustained drug/protein release
behavior.
2.7. Other Compounds
In addition to nanostructures of various metals and metal
compounds discussed above, many other nanostructured
materials have also been prepared by the microwave-assisted
method in aqueous solution. For the microwave-assisted
synthesis of nanostructured metal hydroxides, a water-soluble
metal salt, an alkali as a precipitator, and sometimes an additive
are used in aqueous solution under microwave irradiation.
Umar et al.361 adopted a microwave-assisted hydrothermal
process for the preparation of Mg(OH)2 hexagonal nanodisks
using Mg(CH3COO)2, HMTA, and NaOH (pH 8.5) in
aqueous solution at 160 °C for 15 min. By using as-synthesized
Mg(OH)2 hexagonal nanodisks, an efficient ethanol chemical
sensor with a high sensitivity was fabricated. Al-Hazmi et al.362
reported the microwave-assisted hydrothermal synthesis of
Mg(OH)2 nanosheet-assembled spherical networks and their
utilization for the fabrication of efficient ethanol chemical
sensor, using MgCl2·6H2O, urea, and NaOH as starting
reagents in distilled water (pH 10) at 220 °C for 30 min.
The as-synthesized Mg(OH)2 nanosheet-assembled spherical
networks were composed of the accumulation of hundreds of
nanosheets with thicknesses of ∼95 ± 10 nm. Patra et al.363
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synthesized In(OH)3 nanoparticles in high yields (>95%) using
an aqueous solution containing InCl3 and ammonia under
microwave irradiation in a household microwave oven. α-
GaOOH nanorods were synthesized using Ga(NO3)3, urea, and
L-cysteine (or EDTA disodium salt) in aqueous solution by
microwave heating at 80 °C for 45 min.364
Ni(OH)2 nanoparticles were prepared from an aqueous
solution containing Ni(NO3)2·6H2O and NaOH by microwave
heating at 100 W for 10 min.365 Coralloid nanostructured
nickel hydroxide hydrate was synthesized using NiSO4·6H2O
and urea by a microwave-assisted hydrothermal process at 500
W for 3 min.366 Flower-like α-Ni(OH)2 and β-Ni(OH)2
architectures constructed with nanosheets were synthesized
via the microwave-assisted hydrothermal method. It was found
that the reaction temperature played a critical role in the
formation of the products. Flower-like β-Ni(OH)2 with
monolayer petals and α-Ni(OH)2 with bilayer petals were
prepared at 120 and 150 °C, respectively.367 The microwave-
assisted hydrothermal method was reported for the production
of layered cobalt hydroxide nanocones intercalated with
dodecyl sulfate ions by using HMTA as an alkaline reagent
and SDS as both a surfactant and a structure-directing agent in
aqueous solution at 100 °C for 1 h. A rolling process of lamellar
hydroxide was proposed for the formation of conical structures
with hollow interiors.368 Single-crystalline β-Co(OH)2 nano-
sheets with an average thickness of ∼10 nm were synthesized
from a layered precursor cobalt(II) acetate hydroxide in
aqueous solution by microwave heating at 100 °C for 20
min. The layered precursor was prepared using Co-
(CH3COO)2·4H2O in mixed solvents of EG and water by
microwave heating at 170 °C for 5 min. Co3O4 nanosheets
were obtained by hydrothermal oxidation of the layered
precursor cobalt(II) acetate hydroxide using H2O2 in aqueous
solution.369
Morales et al.370 prepared amorphous chromium hydroxide
particles by forced hydrolysis combined with microwave
heating by aging both solutions of KCr(SO4)2·12H2O and
Cr(NO3)3·9H2O/K2SO4 with different initial ratios of [Cr3+]/
[SO42−] at the boiling temperature. In the first case, the
particles with sizes in the submicrometer range were obtained.
In the second case, the mean size of particles decreased
drastically from the submicrometer range for [Cr3+]/[SO42−]
ratios of 0.5, 0.8, and 1.0 to the nanometer range for ratios of
1.6 and 2.0. Phuruangrat et al.371 prepared Nd(OH)3 nanorods
with diameters of 20−40 nm and lengths of 200−400 nm using
an aqueous solution containing Nd(NO3)3 and ammonia (pH
10) under microwave-hydrothermal conditions at 150 °C for 1
h. Pr(OH)3 nanorods with a diameter of 12 nm and different
lengths ranging from 50 to 220 nm were prepared using
praseodymium oxide, HNO3, and KOH in aqueous solution via
the rapid microwave-assisted method at 520 W for 1 h.372
The microwave-assisted method has also been adopted for
the rapid synthesis of nanostructured metal fluorides in
aqueous solution. Some examples are discussed below. PrF3
hollow nanostructures with the mean particle size of ∼31 nm
were synthesized using praseodymium oxide, HNO3, NaF, and
ammonia in aqueous solution under microwave refluxing for 20
min.373 Flower-like CeF3 nanostructures assembled with
nanodisks were synthesized using EDTA disodium salt as the
complexing reagent in aqueous solution via microwave heating
for 26 min.374 Lanthanide-doped GdF3 nanostructures were
synthesized using Gd(NO3)3 and NaBF4 in aqueous solution by
a rapid microwave-assisted process for 10 min, and raisin-like
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hierarchical nanostructures constructed from densely packed
nanosheets with an average thickness of ∼20 nm were
obtained.375 Parhi et al.376 reported the microwave-assisted
hydrothermal synthesis of nanostructures of KMF3 (M = Zn,
Mn, Co, Fe) with a cubic morphology. Schäfer et al.377 reported
the microwave-assisted hydrothermal synthesis of lanthanide-
doped RbY2F7 nanocrystals with a mean diameter of ∼60 nm in
aqueous solution at 185 °C for 2 h.
A variety of nanostructured metal phosphates have been
successfully synthesized in aqueous solution by the microwave-
assisted method. Zhou et al. 378 prepared amorphous
magnesium phosphate nanospheres from an aqueous solution
containing MgCl2·6H2O, KH2PO4, and NaHCO3 in a house-
hold microwave oven at 100 W for 5 min, and some
experimental parameters such as the pH value, Mg/P ratio,
and solution composition were investigated. BPO4 nano-
particles were synthesized using H3BO3 and H3PO4 (85%)
under microwave irradiation at powers lower than 640 W and
irradiation time ranging from 2.5 to 5 min, and the particle sizes
of BPO4 nanoparticles obtained under microwave irradiation at
640 and 400 W were 40−90 and 30−60 nm, respectively.379
BiPO4 nanoneedles were synthesized using an aqueous solution
containing Bi(NO3)3·5H2O and NaH2PO4·2H2O by microwave
heating (80% of 800 W) for 15 min.380 TiP2O7 nanoparticles
were synthesized by the microwave-assisted reaction between
TiO(OH)2·0.6H2O and H3PO4 (85%) at 800 W for 5 min, and
it was found that the particle sizes of TiP2O7 nanoparticles
ranged from 20 to 100 nm and varied with the microwave
heating time.381 By using the microwave-assisted hydrothermal
approach, single-phase LiFePO4 could be rapidly synthesized in
aqueous solution for 5 min, and the particle sizes of LiFePO4
were dependent on the microwave-hydrothermal conditions.382
Ekthammathat et al.383 prepared LaPO4 nanorods from LaCl3·
7H2O, Na3PO4·12H2O, and HNO3 in aqueous solution at pH 1
under microwave irradiation at 180 W for 1 h. Monoclinic
CePO4 nanorods with 50 nm in diameter were also synthesized
by a similar experimental procedure.384 Patra et al.385
synthesized hexagonal LnPO4·nH2O (Ln = La, Ce, Nd, Sm,
Eu, Gd, Tb) nanorods/nanowires and body-centered tetragonal
ErPO4·nH2O nanoparticles using aqueous solutions of Ln(III)
nitrate and NH4H2PO4 under microwave-solvothermal con-
ditions at the pH values ranging from 1.8 to 2.2 in a household
microwave oven, and the diameters of the resulting lanthanide
orthophosphate nanowires/nanorods were in the range of 6−
130 nm. LaPO4:Ln (Ln = Ce3+, Eu3+, and Tb3+) nanorods with
diameters from 6 to 30 nm were synthesized using NH4H2PO4
as the phosphorus source in aqueous solution by microwave
refluxing for 20 min.386 YP0.8V0.2O4:Ln3+ (Ln = Eu, Sm, Dy)
nanoparticles were synthesized using Na3VO4, Na3PO4, LnCl3,
and PVP by the microwave-assisted hydrothermal method at
150 °C for 30 min.387
Du et al.388 reported the microwave-assisted hydrothermal
synthesis of molecular sieve AlPO4-5 using Al(OH)3, H3PO4,
and tetraethylammonium hydroxide at temperatures of 150−
160 °C for 7−25 min. The sizes of the microwave
hydrothermally synthesized AlPO4-5 nanoparticles were usually
smaller than those synthesized by the conventional hydro-
thermal method with a long processing time (typically 7 h). Ng
et al.389 addressed the efficient utilization of reactants for
enhanced synthesis of nanosized aluminophosphate molecular
sieve by microwave heating, decreasing or almost eliminating
the related waste. AlPO-18 nanosheets were prepared by a
multicycle synthesis approach via reusing nonreacted com-
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pounds from precursor suspensions with minimal requirement
of chemical compensation after recovering of crystalline
nanoparticles from each step. This approach is environmentally
benign, and the organic templates and phosphorous acid can be
almost completely consumed without disposing these harmful
reagents to the environment. Also, the use of microwave
irradiation leads to the preparation of the product within 5 min,
instead of 3 days by the conventional heating.
Square-brick-like CuC2O4 was synthesized using CuCl2 and
K2C2O4 in the presence of sodium dodecyl benzenesulfonate by
a microwave-assisted aqueous solution route at 160 W for 30
min. The CuC2O4 square brick consisted of a large number of
nanoparticles in the middle and a thin nanosheet layer at the
outside surface.390 BaCO3 superstructures formed by the self-
assembly of nanoflakes were synthesized employing BaCl2·
2H2O and NaHCO3 in the presence of SDS in aqueous system
via rapid microwave refluxing for 15 min.391 SrCO3 with a
flower-like or bundle-like morphology was synthesized using
Sr(NO3)2 and (NH4)2CO3 in aqueous solution by the
microwave-assisted method at 90 °C.392 Pb3(CO3)2(OH)2
nanoparticles were prepared using Pb(NO3)2 and urea in
aqueous solution under microwave irradiation, and the reaction
time was drastically shortened to 17 min from 4 h of the
conventional water bath heating method.393
Mahapatra et al.394 prepared nanoparticles of lanthanide
orthovanadates CeVO4, PrVO4, and NdVO4 with sizes in the
range of 25−30 nm by microwave heating. The degradation
rates of dyes and organics in the presence of microwave-
synthesized orthovanadates under UV irradiation were higher
as compared to those synthesized by the solid-state technique.
Fe2(MoO4)3 nanosheet (∼40 nm thick) stacked nanostructures
were fabricated adopting Fe(NO3)3·9H2O as the iron source
and (NH4)6Mo7O4·4H2O as the molybdenum source in
aqueous solution by a microwave-assisted process at 150 °C
for 1 min.395
Ca6Si6O17(OH)2 nanobelts were synthesized by the micro-
wave-assisted hydrothermal method at 180 °C for 90 min
independent of the feeding molar ratio of Ca(NO3)2·4H2O to
Na2SiO3·9H2O in the range of 0.8−3.0. β-CaSiO3 nanobelts
were obtained by microwave heating the powder of
Ca6Si6O17(OH)2 nanobelts as the precursor and template at
800 °C for 2 h. The morphology and size of Ca6Si6O17(OH)2
nanobelts could be well preserved during the microwave
thermal transformation process.396 Bi 6 O 6 (OH)3 (NO 3 ) 3 ·
1.5H2O nanosheets with thicknesses of 50−60 nm were
synthesized using an aqueous solution containing Bi(NO3)3·
5H2O and NaOH (pH 7) via the microwave-assisted
hydrothermal method at 160 °C for 1 h.397 CaSb2O5(OH)2
nanocrystals with sizes of 5−10 nm were synthesized using
CaCl2 and K2H2Sb2O7 via the microwave-hydrothermal
method at 120−180 °C for 20 min. The as-prepared sample
had a higher photocatalytic activity than that of P25.398 A
microwave-assisted two-step hydrothermal procedure was
reported for the preparation of a variety of zeolite
nanostructures. The reaction solution was first treated at 80
°C for 1.5 h under microwave irradiation, and then the
temperature was increased to facilitate the crystal growth.399
Zeolite nanospheres with various organosilanized surfaces were
synthesized in situ by the microwave-assisted method, and the
as-prepared zeolite nanospheres were aggregates of primary
nanoparticles with sizes of ∼10 nm.400
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2.8. Inorganic/Inorganic Nanocomposites
A nanocomposite is a multiphase solid material where at least
one of the constituent phases has one, two, or three dimensions
of less than 100 nm.401 It is usually the solid combination of a
bulk matrix and nanodimensional phase(s) differing in
properties due to differences in structure and chemistry. The
properties of the nanocomposite will differ markedly from
those of the component materials. The promise of nano-
composites lies in their multifunctionality, the possibility of
realizing a unique combination of properties that is not
achievable with traditional materials. The challenges in realizing
this promise are tremendous, which include the control over
the distribution in size and dispersion of the nanosized
constituents, tailoring, and understanding the role of interfaces
between structurally or chemically different phases on bulk
properties.401 The field of nanocomposite materials has
received much attention, imagination, and investigation of
researchers in recent years, which results from the simple
premise of using building blocks with dimensions in the
nanosize range to design and create new materials with
unprecedented flexibility and improvement in the properties.
Because the constituents of a nanocomposite have different
structures and chemical compositions and hence properties,
they serve various functions; thus, the nanocomposite is
multifunctional. Taking some clues from nature and based on
the demands of emerging technologies, which require new
materials for satisfying several functions at the same time in
many applications, scientists have been devising synthetic
strategies for the synthesis of various nanocomposites.401
Microwave-assisted methods are especially advantageous for
producing nanocomposites in terms of simplicity, rapidness,
low cost, and energy saving.
Much effort has been devoted to the microwave-assisted
rapid synthesis of inorganic/inorganic nanocomposites in
aqueous solution. A variety of inorganic/inorganic nano-
composites have been reported, including Pd/Au,402 Pt/
Au,402 Pt/C,403−405 Ag/C,406,407 PtNi/C,408 PtCo/C,409 Se/
C,410 Pt/carbon nanotubes,411 metal/graphene,412−416 Au/
graphene oxide,417 carbon nanotubes/graphene oxide,418 Au/
SiO2,419,420 Au/ZnO,421,422 Ag/SnO2,423 Ag/TiO2,424,425 Cu/
iron oxide,426 C/SnO2,427 C/ZnO,428 C/Fe3O4,429 C/LiMPO4
(M = Mn, Fe, and Co),430 carbon nanotubes/ZnO,431 carbon
nanotubes/MnO2,432,433 carbon nanotubes/RuO2,434 gra-
phene/SnO2,435 graphene/ZnO,436 graphene/iron oxide,437
graphene/Co3O4,438 graphene/carbon nanotubes/SnO2,439
carbon nanotubes/ZnS,440 carbon nanotubes/ZnxCd1−xS,441
graphene/ZnS,442 graphene/CdS,443 graphene/TiO2,444 LiFe-
PO4/C/graphene,445 α-Fe2O3/ZnO,446 Co3O4/CoO,447 ZrO2/
Al2O3,448 RuO2·xH2O/TiO2,449 Bi2O3/Bi2CrO6,450 ZnO/zinc
aluminum hydroxide, 451 ZnO/CdS, 452 ZnO/ZnS, 453,454
Pb3O4/CdS,452 CdO/CdS,455 SiO2/CdS,456 ZnO/ZnSe,457
Cd(OH)x/CdSe,458 ZnS/ZnS:Ag,459 CdS/CdSe,325,460 ZnS/
CdSe,461 CdS/CdTe, 462 CdSe/CdTe,463 CdSeS/ZnS,464
CdSeTe/ZnS/SiO2,465 Mn:ZnSe/ZnS,466 CdSe/CdS/ZnS,325
CdTe/CdS/ZnS.467 Ag/AgCl,468 and nickel boride/MgO.469
Metal/metal alloy or core/shell nanostructures have been
prepared by the rapid microwave-assisted methods in aqueous
solution. Belousov et al.402 reported the reduction of
chlorocomplexes of Au(III) from muriatic solutions by
nanopowders of Pd and Pt at 110 and 130 °C under
hydrothermal conditions and microwave irradiation, and
bimetallic nanoparticles with a core/shell structure were
obtained. The as-prepared core/shell nanostructures had a
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core of the metal reductant covered with a substitutional solid
(Au, Pd) solution in the case of Pd, and isolated by a Au layer
in the case of Pt. An example of the Au/Pd system was
demonstrated that the use of microwave irradiation not only
accelerated the preparation of nanoparticles but also obtained
more homogeneous materials in comparison with the conven-
tional heating.
It has been demonstrated that the microwave-assisted
method is suitable for the preparation of carbon-supported
nanostructures in aqueous solution, and a considerable work
has been devoted to this topic. Zeng et al.403 prepared carbon-
supported Pt nanoparticles with an average particle size of 2.2
nm in aqueous solution by microwave-assisted reduction of
H2PtCl6 using sodium citrate as the reducing agent and
stabilizer in the presence of the commercial carbon at boiling
temperature for 1 h. It was found that the presence of citrate
was generally beneficial to the formation of smaller and more
uniform Pt nanoparticles. Liu et al.404 prepared Pt nanoparticles
with a narrow size distribution using Pt(phen)22+ complex
(phen = 1,10-phenanthroline) in aqueous solution by micro-
wave heating at 700 W for 6 min, and Pt nanoparticles/carbon
nanocomposite was obtained using commercial carbon powder.
It was found that the chelating agent improved the Pt particle
size as well as the dispersion of Pt nanoparticles. Hollow carbon
spheres were prepared by combining the hydrothermal method
with intermittent microwave heating, and then Pt nanoparticles
supported on hollow carbon spheres were prepared by the
reduction of H2PtCl6 with formic acid in aqueous solution by
microwave heating.405 Deivaraj et al.408 prepared carbon-
supported PtNi nanoparticles by the reduction of K2PtCl4
and NiCl2·6H2O with hydrazine using PVP as a stabilizer and
in the presence of carbon by microwave heating at 100 W for
10 min. Hwang et al.409 prepared carbon-supported PtCo alloy
nanoparticles with different alloying extents by employing
microwave heating at 100 °C for 1 h. The as-prepared PtCo
alloy nanoparticles were well dispersed on the surface of the
commercial carbon support with a narrow particle size
distribution.
A microwave-assisted hydrothermal reduction/carbonization
solution route was developed for the rapid synthesis of coaxial
Ag/C nanocables using AgNO3 and sucrose in deionized water
at 200 °C for 20 min, and the nanocables could self-assemble in
situ in an end-to-end fashion into interconnected chains.407
The nanocomposite of carbon spheres with Ag nanoparticles
was prepared from an aqueous solution containing nanoporous
carbon spheres, Ag(NH3)2+ and PVP, the nanocomposite was
synthesized in high yield within a short reaction time, and the
size, number density, and to some extent even the locations of
Ag nanoparticles in/on carbon spheres could be controlled by
adjusting experimental parameters.406 The Se/C nanocompo-
site with a core−shell structure was prepared using starch and
H2SeO3 in deionized water through a microwave-hydrothermal
process at 200 °C for 30 min; the product consisted of Se
nanorod assemblies as the core and an amorphous carbon as
the shell.410
The graphite/SnO2 nanocomposite was prepared by micro-
wave-assisted urea-mediated homogeneous hydrolysis of SnCl4
in aqueous solution at 85 °C for 3 min, and the as-prepared
SnO2 nanoparticles had a narrow size distribution (1−3 nm,
mean: 2.1 nm).427 The carbonaceous species/ZnO nano-
composite was synthesized using an aqueous solution
containing 0.01 M Zn(NO3)2·6H2O, 0.01 M HMTA, and
0.002 M L-(+)-ascorbic acid by a microwave-assisted hydro-
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thermal reaction at 180 °C for 30 min. The nanocomposite
consisted of quasi-single crystalline ZnO regions and
amorphous carbonaceous regions.428 Murugan et al.430
reported the microwave-hydrothermal synthesis of carbon-
coated LiMPO4 (M = Mn, Fe, and Co) nanocomposite
involving in situ carbonization of glucose. An aqueous solution
containing LiOH, H3PO4, glucose, and the sulfate of Mn2+,
Fe2+, or Co2+ was adopted. With a significantly shortened
reaction time as compared to the reported synthetic methods,
the microwave-assisted hydrothermal method offers advantages
of being rapid, cost-effective, and energy-saving.
Carbon nanotubes have been a hot research topic in recent
years due to their excellent properties and promising
applications in various fields. Carbon nanotubes have also
been adopted as the matrix for a variety of nanostructures
prepared by rapid microwave-assisted approaches in aqueous
solution. Wu et al.411 prepared Pt nanoparticles dispersed on
multiwalled carbon nanotubes by microwave heating at 1000 W
with a mode of on for 20 s and off for 60 s for six times. Sun et
al.418 reported a unique microwave-assisted unzipping process
of multiwalled carbon nanotubes in the solution of H2SO4/
H3PO4/KMnO4 for the synthesis of graphene oxide nanorib-
bons, forming core/shell heterostructures. This process was
rapid with a total microwave heating time of 6 min. Potirak et
al.431 synthesized the nanocomposite of carbon nanotubes/
ZnO via a microwave-assisted process using Zn(CH3COO)2·
2H2O and preformed multiwalled carbon nanotubes. ZnO
nanoparticles with sizes of ∼15 nm were dispersively coated on
the surface of carbon nanotubes. The nanocomposite prepared
by microwave heating was much better than that obtained by
the conventional annealing. The nanocomposite of MnO2
nanoplates/multiwalled carbon nanotubes was prepared using
preformed carbon nanotubes, MnSO4·H2O, (NH4)2S2O8, and
(NH4)2S2O4 in aqueous solution under microwave irradiation
at 700 W for 16 min.433 The nanocomposite of aligned carbon
nanotubes/MnO2 was fabricated using KMnO4 and aligned
carbon nanotubes in aqueous solution under microwave
irradiation using a household microwave oven at 700 W for 5
min.432 The nanocomposite of multiwalled carbon nanotubes/
RuO2 was prepared using RuCl3 as the Ru source and NH3·
H2O as a precipitator in the presence of commercial carbon
nanotubes in aqueous solution by microwave heating at 700 W
for a short period of time (30 s). RuO2 nanoparticles were
located both inside and outside of the carbon nanotubes.434
The multiwalled carbon nanotubes wrapped with face-centered
cubic ZnS nanoparticles were prepared using Zn(CH3COO)2
and thioacetamide in aqueous solution under microwave
irradiation at 280 W for 15 min. The dispersion, morphology,
ratio of loading, and size of ZnS nanoparticles in the range of
11.7−24.5 nm could be controlled by adjusting the microwave
power, initial concentration of Zn(CH3COO)2, and molar
ratios of Zn(CH3COO)2/thioacetamide and Zn(CH3COO)2/
carbon nanotubes.440
Graphene has aroused much interest in recent years due to
its excellent properties and promising applications in various
fields. Graphene has also been adopted as the matrix for a
variety of nanostructures. Jasuja et al.417 prepared the
nanocomposite of Au nanostructures on graphene oxide sheets,
which was synthesized by microwave exposure (1.05 kW) on an
aqueous solution of graphene oxide and HAuCl4·3H2O for a
time interval between 1 and 5 min with intermittent cooling
after every 10 s, resulting in the formation of Au nanostructures
with triangular, hexagonal, and dendritic morphologies, which
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either assembled on or were wrapped with graphene oxide
sheets, depending on the microwave exposure time. Zhang et
al.415 prepared the nanocomposite of Pd nanoparticles/
graphene using tannic acid as a reducing agent in aqueous
solution by the microwave-assisted method. The preformed
graphene oxide, H2PdCl4, and tannic acid were adopted as the
starting reactants. The reaction system was heated by
microwaves at 750 W for 1 or 2 min. The loading amount
and size of Pd nanoparticles on graphene sheets could be
controlled by the ratio of raw materials and microwave
irradiation time. It was found that the electrocatalytic activity
and stability of the Pd/graphene nanocomposite were much
better than those of commercial Pd/C catalysts toward
methanol electrooxidation in alkaline media. Siamaki et al.414
prepared Pd nanoparticles with small particle sizes of 7−9 nm
supported on graphene by microwave-assisted chemical
reduction of the corresponding aqueous mixture of palladium
nitrate, hydrazine hydrate, and dispersed graphite oxide sheets
(Figure 13). The reaction mixture was microwave-heated at a
Figure 13. TEM micrographs of (a) 7.9 wt % Pd/graphene and (b)
6.4 wt % Pd/graphite oxide prepared by microwave heating a mixture
of graphite oxide and palladium nitrate in the presence and absence of
hydrazine hydrate, respectively. Reproduced with permission from ref
414. Copyright 2010 Elsevier Inc.
full power (1000 W) in 30 s cycles for a total reaction time of 1
min. The TEM micrographs in Figure 13 show the presence of
well-dispersed uniform Pd nanoparticles on both graphene and
graphite oxide sheets over large areas of several micrometers.
However, Pd nanoparticles supported on graphene were
smaller than those supported on the graphite oxide sheets.
The average particle sizes of Pd nanoparticles supported on
graphene and graphite oxide were determined to be 7−9 and
12−15 nm, respectively. The mean size of Pd nanoparticles
dispersed on graphene and graphite oxide was 8 and 14 nm,
respectively. There was more agglomeration of Pd nano-
particles on graphite oxide than on graphene.
Hassan et al.412 reported the microwave-assisted chemical
reduction preparation of metal nanoparticles (Pd, Cu, Cu/Pd)
dispersed on graphene sheets. This method allows rapid
chemical reduction of exfoliated graphite oxide using a variety
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of reducing agents such as hydrazine hydrate in either aqueous
or organic media. It also allows the simultaneous reduction of
graphite oxide and a variety of metal salts, thus resulting in the
dispersion of metallic and bimetallic nanoparticles supported
on graphene sheets. The Sn/graphene nanocomposite was
prepared using SnCl4·5H2O, urea, and graphite oxide in
aqueous solution by the combination of the microwave-
hydrothermal process at 120 °C for 20 min and one-step
hydrogen gas reduction at 300 °C for 2 h.416 Graphene-
supported PdPt3 nanoparticles were prepared using graphene
oxide sheets, PdCl2, K2PtCl4, CTAB, NaOH, and ascorbic acid
as a reducing agent at pH 9 via microwave heating at 200 W for
4 min.413
The nanocomposite consisting of graphene sheets with only
a few layers and embedded SnO2 nanoparticles with sizes of 4−
5 nm was prepared using SnCl2·2H2O, HCl, and graphite oxide
in aqueous solution by the microwave-assisted hydrothermal
method at 120 °C for 5 min; and subsequently the obtained
SnO2/graphite oxide was reduced by H4N2·H2O in NaOH
aqueous solution by microwave heating at 120 °C for 15
min.435 The nanocomposite of SnO2/reduced graphene oxide/
carbon nanotubes was obtained using graphene oxide, carbon
nanotubes, and SnCl4·5H2O in aqueous solution by the
microwave-assisted hydrothermal method at 150 °C for 10
min.439 The graphene/ZnO nanocomposite was prepared using
ZnSO4·7H2O and NaOH in aqueous solution (pH 9) via
microwave-assisted reduction in the presence of graphite oxide,
and the reaction mixture was microwave-heated at 150 °C for
30 min. The as-prepared product consisted of graphene sheets
decorated densely with ZnO nanoparticles with diameters of
5−10 nm.436 The nanocomposite of reduced graphene oxide/
Fe2O3 was prepared by a two-step process using an aqueous
suspension containing FeCl3, urea, graphene oxide, and
hydrazine by homogeneous precipitation and subsequent
reduction of graphene oxide with hydrazine under microwave
irradiation to yield reduced graphene oxide platelets decorated
with Fe2O3 nanoparticles.437 The graphene/Co3O4 nano-
composite with a homogeneous distribution of Co 3 O 4
nanoparticles (3−5 nm) on graphene sheets was synthesized
using cobalt nitrate hexahydrate and urea in aqueous solution
by microwave heating at 700 W for 10 min.438
The graphene/ZnS nanocomposite was prepared in aqueous
medium under microwave irradiation at 85 °C for 20 min. This
process involved the reactions of graphene oxide nanosheets,
Zn(CH3COO)2, and thioacetamide as well as a reducing agent,
resulting in the formation of ZnS nanoballs with an average
diameter of 41.9 nm supported on graphene nanosheets, and
ZnS nanoballs were composed of many self-assembled ZnS
nanocrystals with an average size of 3 nm.442 The reduced
graphene oxide/CdS nanocomposite was prepared via micro-
wave-assisted reduction of graphite oxide at 150 °C for 10 min
in a solution containing Cd(NO3)2, CH4N2S, graphite oxide,
and NaOH (pH 9).443 A similar microwave-assisted synthesis
was reported for the reduced graphene oxide/TiO2 nano-
composite.444
Various nanocomposites of metal/metal oxide and metal
oxide/metal oxide have been synthesized by rapid microwave-
assisted approaches in aqueous solution. Gu et al.419 prepared
highly dispersed Au nanoparticles with diameters of 5−10 nm
incorporated into pore channels of mesoporous silica SBA-15 in
an aqueous solution of HAuCl4 under microwave irradiation at
700 W for 1 min. Au/SnO2 core−shell nanoparticles were
synthesized using the microwave-hydrothermal method, and
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the formation of the SnO2 shell on the surface of Au
nanoparticles was faster (∼5 min) than that with the
conventional hydrothermal method.420 Kundu et al.421 reported
the microwave-assisted synthesis of the Au/ZnO nano-
composite. The preformed ZnO nanorods grown by the
hydrothermal method exhibited a hexagonal prismatic
morphology. Microwave irradiation (800 W, 3 min, ∼100
°C) of an aqueous solution containing ZnO nanorods and
HAuCl4 resulted in the formation of Au nanoparticles dispersed
on the surface of ZnO nanorods. Geng et al.422 synthesized the
hollow doughnut-like Au/ZnO nanocomposite using Zn-
(NO3)2·6H2O, HAuCl4, HMTA, and trisodium citrate through
a microwave-assisted hydrothermal route at 100 °C for 30 min,
and other different nanocomposites such as ZnO nanorods/Au
nanoparticles, ZnO nanodisks/Au nanoparticles, and ZnO
nanospheres/Au nanoparticles were also obtained by adjusting
experimental conditions. The hollow spheres of Ag/TiO2
nanocomposite were prepared by a template-free microwave-
hydrothermal process, followed by a photochemical reduction
process under the xenon lamp irradiation.424 Li et al.425
prepared the Ag/TiO2 nanocomposite consisting of Ag
nanoparticles (∼5 nm) and TiO2 with various Ag/Ti molar
ratios using preformed TiO2 by the microwave-assisted method.
As compared to the hydrothermal method, the Ag/TiO2
nanocomposite with smaller crystallite size and higher
crystallinity could be obtained by the microwave-assisted
method. Wong et al.426 reported the microwave-assisted
synthesis of copper-doped and 64Cu-doped iron oxide core/
shell nanoparticles with a dextran coating and with diameters
between 20 and 100 nm; FeCl3·6H2O, reduced dextran, FeCl2·
4H2O, CuCl2, and NH3·H2O were used as the starting reagents
in aqueous solution. Reaction times were significantly
shortened while yielding similar sized particles by microwave
heating, and the size of nanoparticles could be controlled
simply by the microwave heating time or by the maximum
power. Al-Tuwirqi et al.447 reported the microwave-hydro-
thermal synthesis of Co3O4/CoO nanorods with an average
length of around 80 nm and an average diameter of 42 nm
using cobalt acetate dehydrate and NaOH in aqueous solution
at 200 °C for 10 min. Prete et al.448 prepared ZrO2-doped (5
mol %) Al2O3 nanopowder using AlCl3·6H2O, ZrOCl2·8H2O,
and NaOH in aqueous solution by the microwave-hydro-
thermal method. Hu et al.449 synthesized the RuO2·xH2O/TiO2
nanocomposite from a solution containing TiCl3, RuCl3·xH2O,
and NaNO3 through a microwave-assisted hydrothermal
process at 150 °C for 10 min. Zhang et al.450 fabricated
Bi 2 O 3 /Bi 2 CrO 6 composite nanowires using Bi(NO 3 ) 3 ,
Na2CrO4, and HCl (pH 1−5) by the microwave-assisted
hydrothermal method at 180 °C for 1 h, and the diameters of
the composite nanowires varied from 30 to 100 nm.
The nanocomposites of metal chalcogenide/metal oxide have
also been prepared by the rapid microwave-assisted method in
aqueous solution. Hu et al.453 demonstrated the microwave-
assisted refluxing synthesis of ZnO/ZnS core−shell nanorods
via in situ surface sulfidation of ZnO nanorods. ZnO nanorods
were prepared by the conventional heating method and used as
the template. By using this method, a layer of ZnS nanoparticles
was deposited onto ZnO nanorods, while retaining the shape of
the original ZnO nanorods, and the thickness and particle size
of the ZnS shell could be adjusted by the concentration of
thioacetamide as the sulfur source. Chen et al.454 used the
microwave-hydrothermal method to synthesize hollow ZnO
core/ZnS shell nanostructures using Zn(NO3)2·6H2O, thiour-
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ea, and dodecylamine at 130 °C for a designated period of time
(1−50 min) with an initial microwave power of 150 W. The
morphological evolution first underwent a process from
precursor flakes to ZnO truncated hexagonal pyramids, and
then toward ZnO hexagonal twin crystals, and the bipods
immediately grew up into solid peanuts, followed by inner
dissolving to form hollow ZnO core/ZnS shell nanostructures.
Cho et al.457 prepared the ZnO/ZnSe porous nanocomposite
by a two-step microwave-assisted hydrothermal process. Porous
ZnO nanostructures were synthesized using Zn(NO3)2·6H2O,
HMTA, and L-(+)-ascorbic acid in aqueous solution via a
microwave-assisted hydrothermal process at 120 °C for 2 h, and
then porous ZnO nanostructures were converted into porous
ZnO/ZnSe nanocomposite by a microwave-assisted dissolu-
tion−recrystallization process using an aqueous solution
containing Na2SeO3 and N2H4·H2O at 160 °C for 2 min.
ZnO and ZnSe were well-mixed (rather than forming core−
shell structures) in the nanocomposite, particularly in the outer
regions. Yang et al.455 prepared CdO/CdS porous core−shell
nanoboxes by microwave-assisted in situ surface sulfidation of
CdCO3 nanocubes using thioacetamide as the sulfur source in
aqueous solution followed by annealing treatment.
Metal chalcogenide/metal chalcogenide nanocomposites
have also been prepared by the microwave-assisted method in
aqueous solution. Jian et al.459 deposited the ZnS shell on the
surface of preformed ZnS:Ag nanocrystals using Zn-
(CH3COO)2·2H2O, NaOH, and 3-mercaptopropionic acid
(MPA) by the microwave-assisted epitaxy growth at 600 W
for 3 min. Growth of the ZnS shell was induced by thermal
decomposition of the Zn−MPA complex under microwave
irradiation. The quantum yield of nanocrystals was significantly
enhanced after the shell growth. Qian et al.460 reported the
seed-mediated microwave-assisted synthesis of alloyed CdSe/
CdS quantum dots in aqueous phase at 140 °C for 5−60 min.
CdSe seeds were first obtained by the reaction between NaHSe
and Cd2+ ions, and then CdSe/CdS quantum dots were rapidly
produced under microwave irradiation in the presence of 3-
mercaptopropionic acid as a sulfide source. Schumacher et al.461
reported the microwave-assisted aqueous synthesis of CdSe/
ZnS core−shell quantum dots using Cd−MPA, Zn(NH3)42+ as
the zinc source in the presence of 3-mercaptopropionic acid at
140−170 °C for 45−120 min. He et al.462 synthesized water-
dispersed and highly luminescent CdTe/CdS core−shell
nanocrystals by the microwave-assisted method in aqueous
phase. A short period (5 min) was required to form an
optimum thickness of the CdS shell using the microwave-
assisted synthesis as compared to several days by the
illumination method. Sai and Kong463 reported the micro-
wave-assisted synthesis of mercaptanacid-capped CdTe/CdSe
core/shell quantum dots using CdTe quantum dots, CdCl2,
NaHSe, and 3-mercaptopropionic acid at pH 11.2 in aqueous
solution. They first prepared CdTe core quantum dots by using
CdCl2 and NaHTe in the presence of 3-mercaptopropionic acid
under microwave irradiation at 100 °C for ∼2 min. Zhan et
al.464 reported the microwave-assisted aqueous-phase synthesis
of CdSeS/ZnS core−shell quantum dots. First, CdSeS core
quantum dots were produced by heating a precursor solution
containing CdCl2·2.5H2O, 3-mercaptopropionic acid, and
Na2SeSO3 at 130 °C for 30 min. After purification through
centrifugation, CdSeS core quantum dots were successfully
capped with a ZnS shell through heating a solution containing
Zn(CH3COO)2·2H2O, Na2S, 3-mercaptopropionic acid, and
NaOH at 100 °C for 1 h. Zhu et al.466 prepared Mn:ZnSe core
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Figure 14. Photographic image of cross-linked PVA with various metallic and bimetallic systems: (a) Pt, (b) Pt−In, (c) Ag−Pt, (d) Cu, (e) Pt−Fe,
(f) Pt with higher concentration ratio, (g) Cu−Pd, (h) In, (i) Pt−Pd, and (j) Pd−Fe. Reproduced with permission from ref 473. Copyright 2007
Wiley VCH.
nanocrystals with oleate capping ligand via a microwave-assisted
hydrothermal process at 170 °C for 40 min, and then the core
nanocrystals reacted with mercaptopropionic acid. An addi-
tional ZnS shell was deposited on the outer layer of Mn:ZnSe
to form Mn:ZnSe/ZnS core−shell nanostructures. In a
traditional aqueous synthesis, the growth rate of ZnSe quantum
dots with mercaptopropionic acid capping ligand was slow by
refluxing. The as-prepared Mn:ZnSe/ZnS core/shell nanocryst-
als were investigated to label antibodies for selective detection
of human immunoglobulin G (IgG) based on fluorescence
resonance energy transfer between Mn:ZnSe/ZnS and Au
nanoparticles.
A green and fast approach (5 min) was reported for the
fabrication of Ag/AgCl hybrid nanoparticles with sizes of about
100 nm using AgNO3, NaCl, and beet juice in aqueous solution
by the microwave-hydrothermal approach at 100 °C and a
maximum pressure of 1930 kPa. In this method, beet juice was
adopted as an environmentally friendly reducing reagent, which
is an abundant sugar-rich agricultural produce.468
2.9. Inorganic/Organic Nanocomposites
In recent years, inorganic nanostructure/organic polymer
nanocomposites have received much attention due to their
interesting properties and promising applications in various
fields. In these nanocomposites, inorganic nanoparticles with
high specific surface areas and unsaturated atoms may interact
with the organic polymer, leading to the enhanced properties of
the nanocomposite. These nanocomposites are considered to
be interesting functional materials with many applications in
various fields. Bogdal et al.19 have published a review article on
the synthesis of polymer−inorganic hybrid nanocomposites
under microwave irradiation, a research area that has made
rapid progress in recent years. They reviewed and discussed the
microwave-assisted preparation and characterization of polymer
nanocomposites composed of layer materials like clays and
layered double hydroxides, metal nanoparticles, and nanowires
as well as carbon-based materials (i.e., fullerenes and nano-
tubes).
It is desirable to develop simple, fast, and low-cost methods
for the synthesis of inorganic/organic nanocomposites from the
technological point of view. The control over the particle size,
size distribution, and dispersity is very important for the
synthesis and application of high-performance nanocomposites.
Conventionally, the polymerization of the organic monomer
and formation of inorganic particles were conducted separately,
and then the polymer and inorganic particles were physically
mixed together, thus the organic polymer and inorganic
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particles were not homogeneously mixed, leading to severe
aggregation of inorganic particles and uneven properties in the
composites. In some cases, relatively high temperatures or
pressures were needed, which made the preparation complex,
difficult, and of high-cost. There have been only a few reports
on the one-step simultaneous formation of inorganic nano-
particles and polymerization of the organic monomer in the
same reaction system for producing high-quality inorganic/
organic nanocomposites.470,471
Kundu et al.472 reported the one-step synthesis of electrically
conductive Au nanowires on DNA in solution and immobilized
on a solid substrate under microwave irradiation for 2−3 min.
DNA served as a reducing and nonspecific capping agent for
the growth of Au nanowires. The as-prepared nanowires were
micrometers long with diameters of 10−15 nm in solution and
of 20−30 nm in immobilized DNA. The nanowires exhibited
ohmic behavior with a low resistance, indicative of continuous
metallic structure.
A variety of metal/polymer nanocomposites were rapidly
prepared in aqueous solution by the microwave-assisted
method. Nadagouda et al.473 reported a microwave-assisted
cross-linking reaction of PVA with metallic and bimetallic
systems in aqueous solution at 100 °C for 1 h. The
nanocomposites of PVA cross-linked metallic systems such as
Pt, Cu, and In and bimetallic systems such as Pt−In, Ag−Pt,
Pt−Fe, Cu−Pd, Pt−Pd, and Pd−Fe were obtained by reacting
the respective metal salt with 3 wt % PVA. Metallic and
bimetallic nanocomposites with various shapes, such as
nanospheres, nanodendrites, and nanocubes, were obtained. A
photographic image of the metallic- and bimetallic-cross-linked
PVA nanocomposites is shown in Figure 14. The cross-linking
and precipitation of PVA occurred for all of the bimetallic
systems: Pt−In, Ag−Pt, Pt−Fe, Cu−Pd, Pt−Pd, and Pd−Fe.
However, except for Pt, In, and Cu, the other metallic systems
such as Ag−, Pd−, and Fe−PVA did not precipitate.
El-Shall et al.474 have developed a facile approach based on
microwave-assisted incorporation of a variety of metallic and
bimetallic nanoparticles within the porous coordination
polymer MIL-101, a chromium-based metal−organic frame-
work with the molecular formula Cr3F(H2O)2O[(O2C)−
C6H4−(CO2)]3·nH2O (where n is ∼25). Metal precursors
and the reducing agent diffused within the pores of the MIL
and adsorbed on the internal and external surfaces of the MIL.
Microwave-assisted reduction for a short period of only 1−2
min resulted in the formation of high concentrations of metal
atoms, which immediately nucleated to form metal nanocryst-
als. The growth of nanocrystals inside the pores was limited by
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the size of the pores, thus resulting in the incorporation of small
nanoparticles with 2−3 nm diameters within the pores. On the
other hand, nanocrystals nucleated on the external surfaces of
the MIL crystals grew larger in size (4−6 nm). The observed
catalytic activities toward CO oxidation of Pd nanoparticles
supported on the highly porous MIL-101 polymer were
significantly higher than those of other reported metal clusters
supported on metal−organic frameworks. Khan et al.475
prepared microgel particles based on poly(N-isopropylacryla-
mide-co-acrylic acid) by emulsion polymerization in the
presence of N,N′-methylenebis(acrylamide). The microwave
heating was adopted for the rapid preparation of highly stable
and monodisperse Ag nanoparticles with an average diameter of
8.5 nm using the microgel as the template via in situ reduction
of AgNO3 in the presence of glucose as a mild reducing agent.
The mixture was heated with a household microwave oven at a
power up to 1.25 kW for only 15 s. The as-prepared Ag
nanoparticles were stable for more than 8 months at room
temperature. Nguyen et al.476 fabricated the nanocomposite
consisting of Ag nanoparticles/PVA nanowires by conjugation
of electrospinning and microwave heating. The 12 wt %
aqueous PVA solutions with and without 2 wt % AgNO3
solution were irradiated for 1 or 1.5 min in a microwave oven.
PVA was used not only as a carrier for loading of Ag
nanoparticles but also as a reducing agent with which the Ag+
ions were reduced to form Ag nanoparticles under microwave
irradiation. Nadagouda and Varma477 reported an environ-
mentally friendly approach for the synthesis of bulk quantities
of the nanocomposites containing transition metals using a
biodegradable polymer, CMC, by reacting respective metal salts
with the sodium salt of CMC in aqueous media. The
spontaneous reduction of noble metals such as Au, Pt, and
Pd could be accomplished using CMC under microwave
irradiation at 100 °C within 5 min in the absence of any
reducing or surfactant agent.
The microwave-assisted preparation method has also been
proved to be effective for a variety of metal oxide/polymer
nanocomposites in aqueous solution. You et al.478 reported the
microwave-hydrothermal synthesis of magnetic Fe3O4/phenol
formaldehyde (PF) core−shell microspheres at 160 °C for 20
min. The structure of the Fe3O4/PF core−shell microspheres
could be well controlled by in situ polycondensation of phenol
and formaldehyde with magnetic Fe3O4 nanospheres as the
seeds in an aqueous solution without any surfactant, and the
shell thickness could be controlled in the range of 10−200 nm.
The as-prepared Fe3O4/PF microspheres were monodisperse
and highly dispersible in water, ethanol, N,N-dimethylforma-
mide, and acetone. Density-controlled ZnO nanoneedle arrays
on a flexible substrate (Teflon) were prepared using Zn-
(CH3COO)2·2H2O, AlCl3, and ammonia in aqueous solution
in the presence of the substrate under microwave irradiation at
95 °C for 30 min, and the density of ZnO nanoneedles on the
substrate could be controlled by adjusting the concentration of
AlCl3.479 The nanocomposite of RuO2·xH2O/poly(3,4-ethyl-
enedioxythiophene) (∼1 wt % RuO2) was prepared via in situ
chemical polymerization of 3,4-ethylenedioxythiophene under
microwave irradiation with a power 900 W within 5 min
followed by thermal treatment in air for 3 h at different
temperatures ranging from 100 to 200 °C.480 Murugan et al.481
reported the rapid synthesis of poly(3,4-ethylenedioxythio-
phene) nanoribbons interleaved between the layers of
crystalline V2O5 under microwave irradiation via a redox
intercalative polymerization reaction of 3,4-ethylenedioxythio-
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phene monomer and commercial crystalline V2O5 in aqueous
solution at different time intervals. As compared to the
conventional refluxing (12 h) for intercalative polymerization,
the microwave-assisted redox polymerization process pro-
ceeded rapidly, enabling the expansion of the interlayer spacing
of crystalline V2O5 from 0.43 to 1.41 nm within 8 min. Jagtap et
al.482 synthesized polyaniline/V2O5 composite nanosheets with
thicknesses of 15−20 nm and with a tremella-like morphology
by in situ intercalation of V2O5 powder and aniline and
subsequent in situ polymerization of aniline in aqueous solution
by the microwave-hydrothermal method at 500 W for 15 min.
Hussein et al.483 reported the microwave-assisted synthesis of
the nanocomposite of Zn−Al-layered double hydroxide/
sodium dodecyl sulfate. They investigated the microwave-
assisted intercalation of anionic surfactant SDS into Zn−Al-
layered double hydroxide to form the nanocomposite.
Spontaneous self-assembly of organic and inorganic component
molecules by the microwave-assisted method was realized in
this study. The effect of the microwave heating time on the
crystallinity and composition of the resulting nanocomposite
was investigated. It was found that the nanocomposites could
be synthesized by microwave heating much faster (0.5−2 h) as
compared to the conventional heating method (3 days).
The microwave-assisted method has been successfully
demonstrated in the rapid synthesis of nanocomposites
consisting of inorganic biomaterials and organic polymers in
aqueous solution. Guha et al.484 reported the post processing of
in situ synthesized HAP/PVA nanocomposite by microwave
heating. They found that the aging time of 1 week required for
the normal biomimetic process was reduced to 1 h under
microwave irradiation. The microwave energy seems to provide
a directional pull to the polymer chains, which leads to an
enhancement of the kinetics of phase formation. Tang et al.485
synthesized the calcium phosphate/polyacrylamide nanocom-
posites with calcium phosphate nanostructures homogeneously
dispersed in the polymer matrix using calcium salt, phosphate,
and acrylamide monomer in aqueous solution by the single-step
microwave-assisted method. The calcium phosphate phase
obtained in a basic medium consisted of hexagonal HAP
nanorods, and HAP nanorods were homogeneously dispersed
in polyacrylamide matrix, while the amorphous calcium
phosphate nanoparticles were formed in a weak acidic medium.
3. MICROWAVE-ASSISTED PREPARATION OF
NANOSTRUCTURES IN POLYOLS
Polyalcohols, such as ethylene glycol (EG), 1,3-propanediol,
1,4-butanediol, and glycerol, have high loss tangents (for
example, EG has a very high loss tangent of 1.350 at 2.45 GHz
and 20 °C); therefore, they belong to the family of strongly
microwave absorbing solvents, and thus are excellent solvents
for microwave-assisted synthesis of inorganic nanostructures.
Polyalcohols are able to form hydrogen bonds extensively,
leading to high viscosities, which in turn correlate with a long
relaxation time.25 The most commonly used polyalcohol is
ethylene glycol due to its much higher dielectric loss and much
higher boiling point as compared to water, and the heating rate
and temperature that can be reached in an open reaction
system are even higher than those in some hydrothermal
processes. Soltani et al.486 reported that ZnS nanocrystals
synthesized with the microwave-polyol method had a higher
degree of crystallinity as compared to that synthesized in water
using the microwave-hydrothermal method.
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Figure 15. Reaction equipment system for the continuous preparation of colloidal metallic nanoparticles by microwave heating: (a) the liquid
column as a pressure regulator, (b) reaction solution container, (c) microwave oven cavity, (d) product suspension receiver, and (e) spiral tube
reactor. For more details, refer to ref 488. Reprinted with permission from ref 488. Copyright 2000 American Chemical Society.

Figure 16. TEM image of the PVP-protected Pt nanoparticles obtained by the microwave-assisted polyol method and the corresponding histogram
of the size distribution of Pt nanoparticles. Reprinted with permission from ref 490. Copyright 2007 Elsevier B.V.

3.1. Metals, Semimetals, Nonmetals, and Alloys
In the polyol process, the polyol can be used as both the
solvent and the reductant; therefore, in many cases, no
additional reducing reagent is needed in the reaction system.
In contrast, a reductant is usually necessary for the preparation
of metal nanostructures in aqueous solution. When EG is used
as the solvent and reductant, metallic nanostructures (M) are
produced by the following chemical reactions according to the
reduction mechanism proposed by Fievet et al.:487
CH 2OH− CH 2OH → CH3CHO + H 2O
CH3CHO + Mn + → M + CH3COCOCH3 + H 2O
By using the microwave-assisted polyol method, many
nanostructures of metals, semimetals, nonmetals, and alloys
have been prepared, including Pt,488−493 Pd,488,490,493−496
Au,497−502 Ag,35,490,503−514 Ru,490,491,515−517 Rh,491 Cu,518−521
Fe,522 Co,523 Ni,524−530 Bi,531 Pt−Ag,493 Au−Pt,502 Au−Pd,502
Au−Ag,502 Au−Rh,532 Pd−Ag,493 Ag−Cu,533 Fe−Ru,534,535
Fe−Pt,534,536,537 Bi−Rh,538 FeNi3,539 Co0.8Ni0.2,540 Se,541 and
Te.542,543
Exciting progress has been made in the microwave-assisted
continuous production of metal nanostructures in liquid phase.
This novel method is promising for large-scale production of
nanostructured materials and their industrial applications. Tu et
al.488 reported the microwave-assisted polyol continuous
production of Pt and Pd colloidal nanoparticles using
H2PtCl6·6H2O or palladium compound, NaOH, and PVP in
the solvent of EG. They designed a microwave-assisted
continuous production reactor, as shown in Figure 15. The
6496
microwave reactor consists of a glass tubing coil with an inner
diameter of 2.8 mm (e) located inside the cavity of a household
microwave oven and a 3.0 L round-bottomed flask containing
the reaction system (b), and nitrogen gas flows to the reaction
system (b); thereby, an adequate pressure is exerted in the
round-bottomed flask. As a result, the reaction solution flows
steadily through the spiral tube (e). The flowing rate of the
solution and thus the microwave heating time of the solution in
the microwave oven cavity can be regulated by changing the
height of the liquid column h (a). After microwave heating, the
resulting colloidal solution flows out of the coil and is collected
by the receiver (d).
In recent years, the microwave-assisted continuous flow-type
preparation of nanostructured materials has been investigated
by several research groups. For example, Nishioka et al.503
reported the continuous preparation of Ag nanoparticles using
a flow-type microwave heating tubular reactor installed in a
cylindrical single-mode microwave cavity using AgNO3, PVP,
and EG based on a polyol process. Ag nanoparticles with
narrow size distributions were synthesized steadily for 5 h,
maintaining almost constant yield (>93%). The microwave
reaction occurred within 2.8 s of residence time, although Ag
nanoparticles were not formed at this flow rate by the
conventional heating. A narrower particle size distribution
was realized by increasing the flow rate of the reaction solution.
Ag nanoparticles with an average size of 9.8 nm and a standard
deviation of 0.9 nm were obtained at a flow rate of 100 mL h−1.
The microwave-assisted polyol continuous flow process was
also reported by other researchers for the preparation of
nanoparticles of noble metals with a narrow size distribution.544
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Rapid and continuous fabrication of Pt nanoparticles was
achieved using a single-mode microwave flow reactor controlled
with a temperature feedback module, and Pt nanoparticles were
obtained under microwave irradiation within 2.8 s of residence
time in glycerol and 1,3-propanediol.489 Groisman and
Gedanken504 developed a continuous circulating flow micro-
wave system that combined reactions in a household
microwave oven with a circulating pump. This system allows
the reagents and products to circulate in and out of the
microwave reactor until the end of the synthesis. The
continuous microwave oven system has several advantages
over the batch microwave oven, such as its ability to work with
large quantity of reagents, the possibility to withdraw the
product without stopping the process, and the constant stirring
of the reagents during the reaction. Various Ag nanoparticles
with different particle sizes were prepared by using this
continuous circulating flow microwave reactor.
As compared to the microwave-assisted continuous flow-type
preparation of nanostructured materials, much more research
has been carried out for the nonflow-type microwave-assisted
preparation. Yu et al.492 reported the rapid microwave-assisted
preparation of polymer-stabilized Pt colloids with a narrow size
distribution in a domestic microwave oven at 750 W for 30 s.
The average diameters of as-prepared Pt colloids varied ranging
from 2 to 4 nm by adjusting the preparation conditions. The
relative standard deviation in diameter of the Pt colloids
synthesized via microwave heating (∼0.17) was much smaller
than that synthesized via the oil bath heating (∼0.3), indicating
that the microwave heating is favorable for the preparation of
narrow size-distributed nanoparticles. Grace et al.490 prepared
uniform and stable polymer-protected spherical Pt, Pd, Ag, and
Ru nanoparticles using glycerol as the solvent and reducing
agent at 290 °C for 2 min in a domestic microwave oven
operated in a cyclic mode. Figure 16 shows a TEM image of the
as-prepared PVP-protected Pt nanoparticles obtained by the
microwave-assisted polyol method and the corresponding
histogram of the size distribution of Pt nanoparticles. The as-
prepared PVP-protected Pt nanoparticles had a narrow size
distribution with a mean particle size of 2.0 nm. A comparative
study was done on the size and morphology of nanoparticles
using different heating modes via the conventional refluxing
and microwave irradiation. The average size of Pt nanoparticles
was 6 nm when the reaction was carried out by the
conventional reflux heating mode (1 h), whereas when the
reaction was carried out by microwave heating mode (2 min), a
decrease in particle size (2 nm) was observed. Similar results
were observed for Pd, Ag, and Ru nanoparticles when these
were synthesized by microwave heating. In addition, in the case
of Pd nanoparticles, triangular nanoprisms were produced in
addition to spherical nanoparticles by microwave heating. A
similar phenomenon was observed for PVP-protected Au
nanostructures prepared using HAuCl4·3H2O and PVP in
glycerol at 290 °C.497
Tsuji et al.498 used the cationic surfactant alkyltrimethylam-
monium bromide (CnTAB: n = 10−16, even numbers) or
cetylpryridinium chloride (C16PC) to modulate the morphol-
ogy of Au nanostructures using HAuCl4·4H2O in the solvent of
EG by a microwave-polyol process for 2 min. They found that
the morphology of Au nanostructures was dependent both on
the chain length of hydrophobic alkyl group and on the
hydrophilic headgroup. Major products were Au spherical
aggregates for CnTAB (n = 10, 12, 14), while triangular,
pentagonal, and hexagonal nanoplates were preferentially
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formed in the presence of C16TAB. Spherical spike-ball
structures were obtained in the presence of C16PC. Au
nanocrystals were obtained in the HAuCl4·4H2O/PVP/EG
and HAuCl4·4H2O/MCl (M = Na, K, H)/PVP/EG reaction
systems by the microwave-polyol method. When HAuCl4·
4H2O was reduced in EG in the presence of PVP at a low
HAuCl4 concentration, mixtures of spherical, triangular,
octahedral, and decahedral Au nanocrystals were obtained in
several minutes. They found that the shape-selective oxidative
etching by AuCl4− + Cl− anions and crystal growth occurred
simultaneously at high HAuCl4 concentrations. The addition of
MCl (M = Na, K, H) was effective to enhance the shape-
selective oxidative etching by AuCl4− + Cl− anions.499 When
di-, tetra-, and poly(ethylene glycol) were heated to 240 °C at a
heating rate of 160 °C/min and held for 5 min, Au icosahedral
nanocrystals with average sizes of 55−85 nm were obtained
from the reaction system of HAuCl4 and PVP in di-, tetra-, and
PEG at high yields (>91%). Plate-like and decahedral particles
were obtained at high yields from the reaction system of
HAuCl4/PVP/NaCl.500 Single-crystalline Au nanorods and
nanowires as well as Au nanostructures with other morphol-
ogies were prepared using HAuCl4·4H2O and surfactants (PVP
and SDS) in EG by the microwave-polyol method at 160 °C.501
Considerable effort has been devoted to the microwave-
assisted preparation of Ag nanostructures in polyols. Li et al.505
adopted the microwave-assisted polyol method for the
preparation of Ag nanoparticles and nanowries in EG at 100
or 150 °C. Ag nanoparticles of ∼10−36 nm and nanowires with
a diameter of 40 nm were obtained. The particle size and shape
of the product could be varied by adjusting the concentration of
the Ag source, PVP molecular weight, and NH4F·HF as a
ligand. By binding Ag+ ions with the ligand, Ag nanoparticles
with larger particle sizes were obtained, and Ag nanowires were
obtained at 100 °C by using F− as a ligand but with relatively
high ratios of ligand/Ag+ and ligand/PVP. Navaladian et al.506
prepared anisotropic Ag nanostructures by decomposition of
silver oxalate in a glycol medium using PVP as a capping agent
under microwave irradiation. It was found that EG was a more
suitable medium than diethylene glycol. Anisotropic Ag
nanostructures were obtained under microwave irradiation for
75 s, whereas spherical nanoparticles with sizes of ∼5−6 nm
formed for 1 min of microwave irradiation. Chen et al.507
prepared Ag nanocubes and nanowires by reducing AgNO3
with EG in the presence of Na2S and PVP. Ag nanocubes could
be obtained by changing the concentration of Na2S and the
heating power. The presence of Na2S had an important effect
on the morphology of Ag nanostructures. When a low
concentration of Na2S solution was used, Ag nanocubes were
produced under different heating powers (300 and 400 W), and
Ag nanowires were obtained at 400 W when a high
concentration of Na2S solution was used. Gou et al.508 reported
the rapid microwave-assisted aerobic polyol preparation of Ag
nanowires with a diameter of 45 nm using AgNO3, NaCl, and
PVP in EG, and the yield of Ag nanowires was 80% in 3.5 min.
Wire formation was highly dependent upon the microwave
heating power, time, and NaCl/AgNO3 ratio. Extended
microwave heating caused the wires to fuse or degrade to
shorter wires presumably via the etching reaction. Kou et al.514
fabricated Ag nanowires using glycerol as both a reductant and
a solvent by a nonstirred microwave-assisted polyol process for
1 min, where SDS was used to prevent the growth of Ag
nanowires. In contrast, no Ag particles were formed at the same
temperature using the conventional heating method. The
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Figure 17. TEM micrographs of Ag nanostructures prepared from AgNO3/H2PtCl6·6H2O (57.5 μM)/PVP (132 mM)/EG at various AgNO3
concentrations at a constant AgNO3/PVP molar ratio of 5.7. Reprinted with permission from ref 510. Copyright 2007 American Chemical Society.
diameter of Ag nanowires could be controlled by changing the
amounts of AgNO3, glycerol, and SDS. When the amount of
SDS was low, the bundles of Ag nanowires were obtained, while
dispersed Ag nanowires formed with a higher SDS amount.
Tsuji et al.509 prepared Ag nanostructures in the presence of
PVP with different molecular weights by the microwave-polyol
method. Ag spherical nanoparticles, nanosheets, polygonal
nanoplates, nanorods, and nanowires were obtained within 8
min. Ag nanosheets and nanoplates were dominantly formed in
the presence of PVP with a shorter chain (10k), while Ag
nanorods and nanowires were preferentially formed using PVP
with a longer chain (40k, 360k). The number density of Ag
nanostructures increased with increasing chain length of PVP.
When AgNO3 was reduced by EG in the presence of Pt seeds
and PVP with a long chain length, Ag nanostructures with
different morphologies were obtained within a few minutes. It
was found that the size and shape of Ag nanostructures were
dependent on experimental parameters such as concentrations
of Pt, PVP, and AgNO3 and heating time. For the preparation
of long nanorods and nanowires at high yields, low Pt
concentrations and high AgNO3 concentrations were required
(Figure 17).510 Figure 17 shows TEM images of the products
obtained in the AgNO3 concentration range of 5.8−92 mM at
constant H2PtCl6·6H2O and PVP concentrations of 57.5 μM
and 132 mM, respectively. At the lowest AgNO3 concentration
of 5.8 mM, only spherical Ag nanoparticles with average
diameters of 42 ± 6 nm were obtained. 1-D Ag nanostructures
were prepared in the 11.5−92 mM AgNO3 concentration
range. The average diameters were similar (∼50 nm) in the low
AgNO3 concentration range of 5.8−46 mM and increased to
∼110 nm at the highest AgNO3 concentration of 92 mM.
These experimental results indicate that 1-D Ag nanostructures
with larger diameters can be prepared at a high AgNO3
concentration. The average length of 1-D Ag nanostructures
increased from ∼120 nm to ∼2.6 μm with increasing AgNO3
concentration from 11.5 to 92 mM. The yield of 1-D Ag
nanostructures increased from nearly zero to 34% when the
AgNO3 concentration was increased from 5.8 to 11.5 mM and
reached ∼60% in the higher AgNO3 concentration range.
Tsuji et al.511 prepared Ag nanorods and nanowires by the
microwave-polyol method for 3 min. Various Pt compounds
such as H2PtCl6 and platinum(II) bis-acetylacetonate were used
to investigate the roles of Pt seeds and anions in the formation
of Ag nanostructures. Furthermore, the effect of Cl− anions on
the morphology of Ag nanostructures was explored by adding
the Cl− additive such as NaCl or KCl in EG solutions
containing AgNO3 and PVP. It was found that the presence of
Cl− ions could accelerate redissolution of formed spherical Ag
particles and was favorable for the growth of 1-D and other Ag
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nanostructures with well-defined crystal structures such as
single-crystalline cubes and twinned bipyramids in the micro-
wave-assisted polyol process. The difference in the adsorption
ability of different species on Ag crystals in solution determined
the shape, size, and yield of Ag nanostructures.512
The microwave-assisted polyol method has also been
adopted for the preparation of Pd nanostructures. Zawadzki494
prepared PVP-stabilized Pd nanoparticles with average sizes
from 2.0 to 15.9 nm using H2PdCl4·nH2O and PVP in various
polyol solvents (EG, diethylene glycol, triethylene glycol)
under microwave solvothermal conditions at 150 °C for 5 min.
The morphology and size of Pd nanoparticles were greatly
affected by the concentration of PVP and Pd salt. The nature of
the reducing agent was of less significance under microwave
solvothermal conditions at fixed parameters (temperature,
pressure, and time); for example, the average size of Pd
nanoparticles obtained using a PVP/Pd molar ratio of 50:1 in
EG, diethylene glycol, and triethylene glycol was 2.0, 3.0, and
3.5 nm, respectively. Yu et al.495 prepared Pd nanocubes and
nanobars with a mean size of about 23.8 nm using H2PdCl4 as
the Pd source, and tetraethylene glycol as both the solvent and
the reducing agent in the presence of PVP and CTAB under
microwave irradiation at 900 W for 80 s, and the effect of
CTAB on the shape of Pd nanocrystals was also investigated.
Pd icosahedra were prepared using H2PdCl4 as the Pd
precursor and PVP as the stabilizer in the presence of an
appropriate amount of KOH in tetraethylene glycol under
microwave irradiation. Pd icosahedra with uniform sizes and
well-defined shapes could be obtained with a yield of over 90%
by microwave heating for 1 min. The sizes of Pd icosahedra
could be controlled by adjusting the concentration of
H2PdCl4.496
Cu nanoparticles with sizes of ∼10 nm were prepared by
reducing CuSO4·5H2O with NaH2PO2·H2O in the presence of
PVP in EG under microwave irradiation for 5 min.518
Hydrazine was also adopted as a reductant for the micro-
wave-polyol preparation of Cu nanoparticles with diameters of
∼15 nm.519 Kawasaki et al.520 obtained Cu nanoparticles with
sizes of ∼2 nm using CuCl2 and NaOH in EG via a microwave-
assisted polyol process at 185 °C for a few minutes without
using additional protective agents. Blosi et al.521 used
diethylene glycol in a microwave-assisted polyol process for
the preparation of Cu nanoparticles. The preparation was
carried out at 60−170 °C for 10 min using Cu(CH3COO)2·
H2O as the copper source in the presence of additives such as
ascorbic acid (reducing agent) and PVP. In the optimum
conditions, Cu nanoparticles with sizes of 46 ± 9 nm could be
obtained. The as-prepared colloidal suspensions were stable for
months despite the high metal concentration.
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Wada et al.524 prepared Ni nanoparticles with a narrow size
distribution through the reduction of Ni(OH)2 with EG under
microwave irradiation, and the average particle size could be
varied between 5 and 8 nm by adjusting the microwave heating
time and power. Eluri et al.525 prepared Ni nanoparticles using
Ni(CH3COO)2·4H2O, NaH2PO2·H2O, and NaOH in propy-
lene glycol under microwave irradiation for 35 s. By varying the
molar ratio of the reactants, Ni nanoparticles with sizes of 3.9−
7.2 nm were obtained. Increasing the concentration of NaOH
resulted in a morphological change from isolated spherical
particles to agglomerated nanoflowers (72 ± 14 nm). Addition
of a small amount of PVP or CTAB resulted in a slight increase
in particle size. Ni nanoparticles with sizes in the range of 30−
100 nm were prepared using PVP and dodecylamine as
protecting agents through a microwave-assisted polyol process
in EG, and the morphology of Ni nanoparticles could be
controlled by the amount of dodecylamine, and the particle size
and size distribution could be adjusted by the concentration of
the metal source and dodecylamine/PVP ratio.526 Donegan et
al.529 prepared Ni nanocrystals with an icosahedral morphology
in EG using the microwave-assisted polyol method. Nickel
acetylacetonate was used as the nickel precursor, while sodium
formate and n-trioctylphosphine oxide were employed as the
reducing agent and capping ligand, respectively. Hu et al.530
prepared Ni nanowires using NiCl2·6H2O, trioctylphosphine
oxide, and hydrazine monohydrate in EG by a rapid microwave-
assisted process at 160 °C for 5 min. Ni nanospheres with sizes
of 5−100 nm, formed by self-assembly of primary nanoparticles
with an average dimension of ∼6.3 nm, were prepared using
NiCl2, Na2CO3, NaOH, hydrazine hydrate, and PVP in EG
under microwave irradiation at 450 W for 1 min.528 Liu et al.527
prepared Ni nanospheres using Ni(CH3COO)2·4H2O in
triethylene glycol by a microwave-assisted polyol refluxing
process.
Chefetz et al.545 developed a combined procedure composed
of adsorption of metallic ions on aquatic plants and conversion
of adsorbed metal ions into metallic nanoparticles in EG by
microwave heating. The combined process offers a promising
approach for the removal of heavy metal ions from the
wastewater and recycling of adsorbed metal ions into metallic
nanoparticles. They used the aquatic plant Azolla as the sorbent
for Ag+, Pb2+, and Ru3+ ions in aqueous solution.
The microwave-assisted polyol method has also been
demonstrated for the rapid synthesis of metal alloy
nanostructures. Du et al.535 prepared Fe−Ru bimetallic
nanoparticles using 1,2-propanediol to reduce the mixture of
FeCl3 and RuCl3 in the presence of PVP as a protective agent
by the microwave-assisted polyol method at 300 W for 3 min.
Köhler et al.538 prepared Bi−Rh pseudohexagonal nanoplates
using bismuth acetate and rhodium acetate dimer in EG by a
microwave-assisted polyol process at 240 °C for 1 h. FeNi3
nanochains were prepared by reducing iron(III) acetylacetonate
and nickel(II) acetylacetonate with hydrazine in EG under
microwave irradiation at 160 °C for 5 min.539 Co0.8Ni0.2
nanostructures were prepared in 1,2-propanediol by a micro-
wave-assisted polyol process, and it was found that rapid
heating led to the formation of nanowires while slow heating
resulted in nanourchins, and the aspect ratio of Co0.8Ni0.2
nanowires decreased with increasing temperature.540
Zhu et al.543 prepared Te nanorods and nanowires using
TeO2 in EG by a surfactant-free microwave-polyol process at
185 °C for 30 min. The aspect ratio of Te nanostructures could
be controlled by adjusting the experimental parameters. The
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yield of Te powder was usually higher than 90%. They also
prepared Se nanorods and nanowires by one-step surfactant-
free microwave-polyol reduction of SeO2 with EG at 195 °C for
30 min.541
In addition to polyols, the polythiol (1,2-ethanedithiol) was
also adopted for the microwave-assisted preparation of
nanostructures. Zhu et al.546 developed a new microwave-
polythiol method using a polythiol (1,2-ethanedithiol) as both a
reducing reagent and a solvent. 1,2-Ethanedithiol has a boiling
point of about 147 °C, much lower than that of its polyol
counterpart (EG with a boiling point of ∼197 °C). By using the
microwave-polythiol method, Te structures with various
morphologies were obtained at relatively low temperatures
(≤140 °C) for 30 min. The morphology of Te could be
controlled by adjusting experimental parameters. In addition,
Ag nanowires were obtained using Ag2O as the silver source
and 1,2-ethanedithiol as both a reducing reagent and a solvent
through a solid−liquid reaction mechanism by the microwave-
polythiol method at temperatures between 80 and 140 °C.547
3.2. Metal Oxides
Microwave-assisted synthesis of metal oxide nanostructures has
aroused much interest due to interesting properties of different
kinds of metal oxides and their wide applications. Usually, a
metal salt is used as the metal source, and an alkali and/or an
additive is adopted in a polyol solvent. Many kinds of
nanostructured metal oxides prepared by the microwave-
assisted polyol method have been reported, including
MgO, 548 ZnO, 549−554 Fe 3 O 4 , 522,555−559 α-Fe 2 O 3 , 560 γ-
Fe2O3,556 CuO,561 Cu2O,561 Co3O4,562 NiO,563 MnO,564
ZnAl 2 O 4 , 565 CoFe 2 O 4 , 566,567 NiFe 2 O 4 , 567 ZnFe 2 O 4 , 567
MnFe 2 O 4 , 5 6 7 Co 1 − x Zn x Fe 2 O 4 , 5 6 8 Mn 1− x Zn x Fe 2 O 4 , 5 6 9
BaTiO 3 , 5 7 0 PbTiO 3 , 5 7 0 Ba 6 Ti 1 7 O 4 0 , 5 7 0 BaZrO 3 , 5 7 0
La0.67Ca0.33MnO3,571 SrWO4,572,573 BaWO4,574
CaMoO4,575,576 SrMoO4,573,576 BaMoO4,574,576 PbWO4,577
PbMoO4,577 Bi2WO6,578 and Y3Al5O12.579 Various polyols
have been adopted as the solvent, including ethylene
glycol,522,548,553,554,556−563,566,568−575,577,578 propylene glycol,576
1,3-propanediol,551 1,4-butanediol,550,565,579 diethylene gly-
col,549,552,555 and triethylene glycol.564,567
Hu et al.552 reported the rapid microwave-polyol synthesis of
ZnO spheres composed of small primary nanocrystals in the
solvent of diethylene glycol with a boiling point of ∼245 °C.
The size of ZnO spheres could be tuned from ∼57 to 274 nm
by simply varying the amount of the Zn complex precursor. In
this method, the Zn(CH3COO)2/diethylene glycol stock
solution (20 mL) was microwave-heated with magnetic stirring
at 180 °C for 5 min to form a slightly turbid solution, which
was used as a seeding solution for further reactions. When
another aliquot of the Zn(CH3COO)2/diethylene glycol stock
solution (20 mL) was microwave-heated to 120 °C within 1
min, the above resulting seeding solution (1.8 mL) was injected
rapidly into this hot mixture, and the temperature was
maintained at 120 °C for 1 min. The reaction temperature
then was promptly elevated to 180 °C and further kept at this
temperature for 5 min to yield ZnO spheres. The amount of the
seeding solution determined the size of ZnO spheres. For
example, the amounts of seeding solution of 2.2, 2.5, 3, 5, 8, and
10 mL produced ZnO spheres with average sizes of 210, 183,
162, 125, 86, and 57 nm, respectively. Liang et al.553
synthesized ZnO nanosheets by decomposition of a layered
precursor, which was synthesized using Zn(CH3COO)2·2H2O
in EG by microwave heating, and the thicknesses of ZnO
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nanosheets were in the range of 5−10 nm. Lojkowski et al.554
prepared ZnO nanostructures doped with Mn2+, Ni2+, Co2+,
and Cr3+ ions by a microwave-solvothermal reaction from an
EG solution containing zinc acetate and acetates of manganese-
(II), nickel(II), cobalt(II), and chromium(III). The average
grain size of the powder doped with 10 mol % Mn2+, Ni2+,
Co2+, and Cr3+ was about 20 nm, and the grain size of doped
ZnO nanostructures decreased with increasing dopant content.
Fe3O4, γ-Fe2O3, or α-Fe2O3 hierarchically nanostructured
hollow microspheres assembled by nanosheets were prepared
by a novel precursor-templated thermal conversion method.
The hierarchically nanostructured hollow microspheres organ-
ized by nanosheets of a layer-structured ferrous precursor were
synthesized using FeCl3·6H2O, NaOH, and sodium dodecyl
benzenesulfonate (SDBS) in the solvent of EG by the
microwave-assisted solvothermal method at 200 °C for 30 or
90 min.556,560 EG acted as both a solvent and a reductant to
reduce ferric salt to ferrous precursor in the presence of NaOH
and SDBS. The hollow microspheres of the precursor were
used as the iron source and morphological template for
subsequent thermal transformation to prepare hierarchically
nanostructured hollow microspheres assembled by Fe3O4, γ-
Fe2O3, or α-Fe2O3 nanosheets. One of the advantages of this
method is that Fe3O4, γ-Fe2O3, or α-Fe2O3 hierarchically
nanostructured hollow microspheres consisting of organized
nanosheets can be synthesized using the same single source
precursor. Hierarchically nanostructured hollow microspheres
assembled by Fe3O4 or γ-Fe2O3 nanosheets were surface
modified with PEG. The hierarchically nanostructured
magnetic hollow microspheres of Fe3O4 or γ-Fe2O3 had a
high drug loading capacity and favorable drug release property
for ibuprofen, with an ibuprofen uptake amount of 297 and 237
mg g−1 for PEG-coated Fe3O4 and PEG-coated γ-Fe2O3,
respectively; thus, they are promising for the application in drug
delivery.556 The as-prepared α-Fe2O3 hierarchically nano-
structured hollow microspheres exhibited a better photo-
catalytic property than that of ringlike nanoparticles and also
showed a satisfactory removal capacity for methyl orange in
wastewater treatment.560
Fe3O4 nanoporous spheres with an average size of ∼100 nm
were synthesized using FeCl3·6H2O, CH3COONa, and PEG in
EG by microwave heating at 200 °C for 5 min.558 The
microwave-assisted polyol approach was adopted for the
synthesis of Fe3O4 nanoroses constructed by nanosheets
using FeCl3·6H2O, CH3COONa, and PEO−PPO−PEO block
copolymer (P123) in EG at 160 °C for 15−60 min.559 Flower-
like Fe3O4 structures formed by self-assembly of nanosheets
were synthesized using the precursors that were prepared using
FeCl3·6H2O, tetrabutylammonium, and CO(NH2)2 in EG
through a microwave-assisted reaction at 120−210 °C for 30
min, and, subsequently, the precursors were thermally treated
in nitrogen at 400 °C for 2 h.522
Staszak et al.565 prepared ZnAl2O4 nanoparticles with a spinel
structure (average crystallite size was 3 nm) using Zn-
(CH3COO)2 and aluminum isopropoxide in 1,4-butanediol
under microwave-assisted solvothermal conditions at 200 °C
for 30 min. Ibrahim et al.566 prepared CoFe2O4 nanoparticles
using Co(NO3)2·6H2O and Fe(NO3)3·9H2O in the solvent of
EG via the microwave-polyol method at 900 W for 2 min.
Solano et al.567 prepared MFe2O4 (M = Fe, Co, Mn, Ni, and
Zn) nanoparticles with diameters smaller than 10 nm by
microwave heating at 220 or 280 °C for 10 min under magnetic
stirring, based on the decomposition of acetylacetonate metal
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precursors in triethylene glycol. Giri et al.568 prepared
Co1−xZnxFe2O4 (0 ≤ x ≤ 0.8) nanoparticles (5−30 nm)
using Zn(CH3COO)2·H2O, Co(CH3COO)2·4H2O, FeCl3, and
KOH in EG by microwave refluxing, followed by calcination at
500 °C for 2 h. The particle size of the product was dependent
on experimental parameters such as the pH value, Zn content,
EG volume, and refluxing time. The pH values of 9−10 were
optimum for the formation of well-dispersed nanoparticles. In
addition, Mn1−xZnxFe2O4 nanoparticles were prepared using
MnCl2·4H2O, FeCl3, ZnCl2, and PEG in EG by microwave
refluxing for 30 min to 3 h, and the morphology and size of the
product were dependent on experimental parameters such as
the pH value, refluxing time, and PEG.569
Palchik et al.570 reported the microwave-assisted synthesis of
nanoparticles of BaTiO3, Ba6Ti17O40, BaZrO3, and PbTiO3
using Pb(CH3COO)2·3H2O, BaCl2, zirconium perchlorate
octahydrate, and titanium isopropoxide as the reactants in the
solvent of EG by microwave refluxing for a relatively long
period of time (1−5 h). Nayak et al. 571 prepared
La0.67Ca0.33MnO3 nanoparticles with sizes of 30−70 nm from
metal acetates in EG by microwave refluxing for 1 h followed by
annealing at different temperatures. Thongtem et al.572
prepared SrWO4 nanoparticles using SrCl2 and Na2WO4 in
EG at different pH values, microwave powers (180−600 W),
and heating times (20−80 min). Bi2WO6 nanosheets were
synthesized using Bi(NO3)3·5H2O and (NH4)10W12O41·5H2O
in EG by a microwave-solvothermal process at 160 °C for
different times (2 or 4 h).578 BaMoO4 nanoparticles (30−75
nm) and BaWO4 nanoparticles (20−75 nm) were synthesized
from the reactions between Ba(NO3)2 and Na2MeO4 (Me =
Mo and W) in EG under 300 W microwave irradiation for 20
min.574 SrMoO4 nanocrystals with sizes of 14−40 nm and
SrWO4 nanocrystals with sizes of 14−38 nm were synthesized
using Sr(NO3)2 and Na2MeO4 (Me = Mo and W) in EG under
microwave irradiation at 50% of 180 W for 20 min.573 CaMoO4
nanoparticles with particle sizes of 16−44 nm were synthesized
from Ca(NO3)2 and Na2MoO4 in EG under pulsed microwave
irradiation at 300 W for 20 min.575 MMoO4 (M = Ba, Sr, and
Ca) nanostructures were prepared by the reactions of
M(NO3)2·2H2O, Na2MoO4·2H2O, and NaOH in propylene
glycol under pulsed microwave irradiation at 600 W for 20
min.576 PbMoO4 (15−50 nm) and PbWO4 (12−32 nm)
nanoparticles were synthesized using Pb(NO3)2 and Na2MO4
(M = Mo and W) in EG under microwave irradiation at 50% of
180 W for 20 min.577
3.3. Metal Chalcogenides
Microwave-assisted polyol synthesis of nanostructures of metal
sulfides, metal selenides, and metal tellurides is very important
for applications of these materials in various fields. In the
microwave-assisted polyol synthesis of nanostructures of metal
chalcogenides in the solvent of a polyol, a metal salt is usually
used as the metal source, and a source of sulfur or selenium or
tellurium and sometimes an additive are adopted. As compared
to the synthesis with the conventional heating methods, the
microwave-assisted synthesis of metal chalcogenide nanostruc-
tures has an obvious advantage of rapidness, with much reduced
preparation time often by orders of magnitude. Many kinds of
nanostructured metal chalcogenides prepared by the micro-
wave-assisted polyol method have been reported, including
SnS,580,581 SnS2,580,581 PbS,582,583 Sb2S3,584,585 Bi2S3,586,587
CdS,588−592 ZnS,591,593,594 CuS,595−597 FeS2,598 CoS,591
Cu 3 BiS 3 , 5 9 9 Cu 2 ZnSnS 4 , 6 0 0 CdSe, 6 0 1 , 6 0 2 β-FeSe, 6 0 3
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Sb 2 Se 3 , 604,605 Bi 2 Se 3 , 606 MoSe 2 , 607 Cd 1−x Zn x Se, 608,609
CuInSe 2 , 610 Sb 2 Te 3 , 611 Bi 2 Te 3 , 612 PbTe, 613 Ni 2 Te 3 , 613
Cu7Te5,613 Cu(2−x)Te,614 and CuInTe2.610 EG has been
commonly adopted as the sol-
vent.580,581,583,584,586−601,606−609,611−614 In addition, other poly-
ols have also been used as the solvents, such as propylene
glycol,582,603 1,2-propanediol,585 triethylene glycol,601,610 1,5-
pentanediol,604 glycerol,602,605,612 and tetraethylene glycol.610
Oliveira et al.588 prepared CdS nanostructures with a
hexagonal crystal structure using CdCl2·H2O and NH2CSNH2
in the solvent of EG or ethylenediamine via the microwave-
assisted solvothermal method at 180 °C for 32 min. It was
found that the solvent had a significant effect on the
morphology of the product. Flower-like CdS nanostructures
constructed with nanosheets (25 nm in thickness) were
obtained in the presence of EG; in contrast, aggregates of
nanoplates (40 nm in thickness) were formed in the solvent of
ethylenediamine.
Recently, some researchers adopted the combination of both
microwave and sonochemical irradiation for the synthesis of
nanostructures in liquid phase. Tai et al.590 prepared CdS
nanoparticles using Cd(CH3COO)2·2H2O, CH3CSNH2, S
powder, and NaCl in EG by an ultrasound−microwave
combined process at 140 °C for 15 min. Zinc blende CdS
nanoparticles were produced in the absence of NaCl, while
mixed zinc blende and wurtzite CdS nanoparticles were
obtained when NaCl/Cd2+ molar ratios were below 1, and
pure wurtzite CdS nanoparticles were produced at a molar ratio
of 1. Tai and Guo589 prepared flower-like CdS nanostructures
consisting of hexagonal nanopyramids and/or nanoplates
depending on the sulfur source by applying ultrasound and
microwave irradiation simultaneously, using the starting
reactants of CdCl2, NH2CSNH2 or C2H5NS, and S powder
in the solvent of EG. The synergistic effect of microwave and
sonochemical irradiation was proposed for the formation of
CdS nanostructured flowers. Ma et al.592 adopted the
ultrasound−microwave combined method to prepare Ag-
doped CdS nanoparticles in EG at 140 °C for 15 min. It was
found that Ag doping of CdS nanoparticles could induce the
evolution of crystal structure from cubic to hexagonal under the
synergistic effect of ultrasound and microwaves.
Wang et al.595 reported the microwave-biomolecule-assisted
synthesis of CuS nanostructures with different morphologies
using CuCl2·2H2O, thiourea, and histidine in EG at 130 or 150
°C for 3−15 min. It was found that histidine played an
important role in the formation of CuS hierarchical
architectures. The morphology and size of the product could
be tuned by adjusting the molar ratio of Cu2+/histidine and
Cu2+/thiourea. Thongtem et al.596 synthesized assemblies of
nanoflakes, nanoparticles, nanofibers, nanorods, and spongelike
structures of CuS from copper and sulfur sources (CuCl2·
2H2O, CuBr, Cu(CH3COO)2·H2O, CH3CSNH2,
NH2CSNHNH2, and NH2CSNH2) in EG under cyclic
microwave irradiation at different microwave powers and
times. Liu et al.597 reported the microwave-assisted solvother-
mal synthesis of CuS nanotubes assembled with nanoparticles
using Cu(OH)2 nanowires and thiourea in the solvent of EG at
80 °C for 10 min to 2 h. ZnS nanoparticles with sizes of ∼3 nm
were prepared using Zn(CH3COO)2·2H2O and Na2S·9H2O in
EG by microwave heating at 65 W for 10 min.593 Hexagonal
phase ZnS nanocrystals with sizes of ∼5 nm were synthesized
by microwave thermolysis of a single-source molecular
precursor of zinc diethyldithiocarbamate in EG at 110 °C for
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5 min.594 FeS2 microspheres were synthesized using FeSO4·
7H2O, PVP, and S powder in EG by microwave-assisted polyol
refluxing for 1 h under nitrogen flow.598 The formation of FeS2
microspheres was proposed via a nanocrystal aggregation-based
mechanism, in which primary FeS2 nanocrystals were first
formed, then they self-assembled into microspheres, and finally
the Ostwald ripening led to the monodisperse microspheres.
Kavinchan et al.584 synthesized orthorhombic Sb2S3 nanorod
bundles with a dumbbell-like morphology using SbCl3,
Na2S2O3, and PVP in the solvent of EG under cyclic microwave
irradiation (600 W, 50 s on and 20 s off) for 15 cycles. Sb2S3
nanorods with diameters ranging from 30 to 50 nm were
synthesized by the reaction between SbCl3 and thiourea in the
presence of PVP in the solvent of 1,2-propanediol via
microwave irradiation for 15 min.585 Nest-shaped Bi2S3
nanostructures were synthesized using CdS mother nanocryst-
als, Bi(NO3)3·5H2O, and CTAB in EG via the dissolution−
recrystallization process by microwave heating in a household
microwave oven at 800 W for 50 s. During the dissolution−
recrystallization process, the growth regime could be controlled
from the thermodynamic control to the kinetic domination
through adding more Bi3+ ions or changing the heating method
from oil bath to microwave heating.586 Bi2S3 flower-like
superstructures consisting of nanorods with average diameters
of 10−20 nm were prepared using Bi(NO3)3·5H2O and
thiourea in EG under microwave irradiation for 3 min.587
Aup-Ngoen et al.599 synthesized nanostructured Cu3BiS3
dendrites using CuCl, BiCl3, and L-cysteine in EG under cyclic
microwave irradiation with powers of 300−700 W, and the
morphology evolution from nanoparticles to nanostructured
dendrites was observed with increasing microwave power.
Flynn et al.600 synthesized Cu2ZnSnS4 nanoparticle inks using
CuCl, ZnCl2 SnCl4·5H2O, and thioacetamide in EG (pH 2) by
the microwave-assisted method at 190 °C for 30 min. The
diameters of Cu2ZnSnS4 nanoparticles were determined to be
7.6 ± 2.1 nm, and these nanoparticles were found to
agglomerate into larger particles.
In addition to nanostructured metal sulfides, nanostructures
of metal selenides have also been prepared by the microwave-
assisted polyol method. Palchik et al.601 reported the
microwave-assisted polyol preparation of CdSe nanoballs
composed of CdSe nanocrystals with sizes of a few nanometers
using Cd(CH3COO)2 and Se powder in the solvent of a polyol.
The crystal phase of the product depended on the polyol used;
the hexagonal CdSe was obtained in EG, and the cubic CdSe
formed in triethylene glycol. Cao et al.602 prepared a variety of
multipod-shaped CdSe nanostructures using Cd(NO3)2 and Se
powder in glycerol via microwave irradiation at 150 °C for 10
min. By selectively introducing organic additives (CTAB, oleic
acid, and PVP) into the system, the morphology of CdSe varied
from tetrapods to hexapods, octapods, and more complex
multipods. Harpeness et al.606 used the microwave-polyol
method to prepare nanostructured Bi2Se3 using BiONO3,
elemental Se, and NaOH in EG for 30 min under nitrogen
environment. Zhao et al.605 prepared Sb2Se3 nanorods with
diameters of 40−70 nm through the reaction between Se
powder and sodium antimony tartrate in glycerol by microwave
heating at 120 °C for 30 min. Mehta et al.604 reported the rapid
and scalable (gram-a-minute) microwave-assisted synthesis of
sulfurized Sb2Se3 nanowires and nanotubes that exhibited about
104−1010 times higher electrical conductivity than bulk or thin
film forms of this material. They adopted a microwave-activated
solvothermal reaction of trin-octylphosphine (TOP)-ligated
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selenium and thioglycolic acid (TGA)-ligated antimony salts in
1,5-pentanediol using a domestic microwave oven (1250 W) or
a variable power single-mode CEM microwave reactor (300
W). They prepared the antimony and selenium precursors by
independently microwave heating the antimony salt in
pentanediol with TGA and selenium with TOP. The sulfur
content was varied by adjusting the TGA/TOP−Se2− molar
ratio. The two precursors were then mixed and microwave
heated for different time intervals between ∼1−2 min. This
synthetic process is easily scalable and yields gram quantities in
a few minutes, for example, 2−3 g in 2 min. Li et al.603 prepared
flower-like tetragonal β-FeSe microstructures assembled from
nanoplates with thicknesses of ∼60−70 nm using FeCl3·6H2O,
Se powder, and NaOH in 1,2-propylene glycol under
microwave irradiation for 1 h.
The nanostructures of doped metal selenides have also been
prepared by the microwave-assisted polyol method. Grisaru et
al.608 prepared Cd0.8Zn0.2Se nanoparticles with an average
diameter of 6 ± 2 nm using Zn(CH3COO)2, Cd(CH3COO)2,
Se powder, and NaOH in EG by a microwave-assisted polyol
process for 1 h, followed by annealing under nitrogen at 550 °C
for 12 h. By using a similar microwave-assisted polyol process,
nanoparticles of Cd1−xZnxSe alloy (x ≈ 0.1, 0.2, 0.3) with
average diameters of 5−8 nm were prepared, and the
nanoparticles formed spherical aggregates with a diameter of
approximately 200 nm.609
The nanostructured metal tellurides have also been prepared
by the microwave-assisted polyol method. Palchik et al.613
prepared nanostructured binary metal tellurides, such as PbTe,
Ni2Te3, and Cu7Te5, by the microwave-assisted polyol method.
Binary tellurides were formed only in the case when EG was
used as a reducing agent under microwave irradiation. No
product was obtained when the reactions were performed by
the conventional heating. A rapid microwave-assisted polyol
route was adopted for the preparation of Sb2Te3 hexagonal
single-crystalline nanoplates using Na(SbO)C4H4O6, Te
powder, and NaOH in EG at 280 W for 45 min.611 A mixture
of Bi2Te3 nanorods and nanoflakes was prepared using
Bi(NO3)2·5H2O, Te powder, and KOH in EG or glycerol via
the microwave-assisted polyol method.612 Cu(2−x)Te single-
crystalline nanowires were prepared employing Te nanotubes
as the reactive and self-sacrificial template in EG by a
microwave-assisted solvothermal process at 200 °C for 1 h.614
Grisaru et al.610 prepared nanoparticles of CuInTe2 (∼100 nm)
and CuInSe2 (∼85 nm) by the microwave-assisted polyol
method. For the preparation of CuInSe2, CuCl, In, and Se were
used as the reactants, and triethylene glycol was used as the
solvent. For the preparation of CuInTe2, the preparation
procedure was similar to that of CuInSe2, and Te was used
instead of Se, and tetraethylene glycol was used as the solvent.
3.4. Other Compounds
A small number of nanostructures of other compounds have
also been prepared by the microwave-assisted polyol method,
and some examples include fluoride,615−617 bromide,618,619
hydroxide,620 sulfate,621 carbonate,392,622,623 phosphate,616,624
silicate,625 molybdenate,626 and tungstate.627
Polyethylenimine (PEI)-doped LaF3 nanoparticles were
synthesized using corresponding metal nitrates (or chlorides)
and NaF in EG via the microwave-assisted polyol method at
120 or 150 °C for 30 min. The as-prepared nanoparticles had a
hexagonal structure with an average size of about 12 nm. When
doped with different ions (Ce3+/Tb3+ or Eu3+), the morphology
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and structure of the nanoparticles did not change, whereas the
optical properties varied with doped ions and their molar ratio,
and as a result emissions of four different colors (green, yellow,
orange, and red) were achieved by simply changing the types of
doping ions (Eu3+ and Tb3+) and the molar ratio of the two
doping ions.615 The combination of the rapid microwave
heating and the microfluidic reactor is advantageous for
continuous production of nanostructured materials with high
yields. Zhu et al.616 utilized a microfluidic reactor heated by
microwaves to prepare LaF3:Ce,Tb nanoparticles with a mean
diameter of 4.5 nm and LaPO4:Ce,Tb nanorods with diameters
of 10−15 nm and lengths of 60−70 nm using EG as the
solvent. BiOBr microspheres formed by self-assembly of
nanosheets were obtained using Bi(NO3)3·5H2O and CTAB
in the solvent of diethylene glycol via the microwave-assisted
solvothermal method at 180 °C for 10 min.618 Flower-like
BiOBr nanostructures were prepared using Bi(NO3)3·5H2O
and CTAB in mannitol through a microwave-assisted process at
110 °C for 27 min. CTAB acted as both the bromide source
and the soft template. Different flower-like BiOBr nanostruc-
tures could be obtained by varying the CTAB concentration.
The as-prepared flower-like BiOBr nanostructures exhibited a
high removal capacity and fast adsorption rate for Cr6+ ions in a
wide pH range.619
Li et al.621 prepared CaSO4·0.5H2O single-crystalline nano-
wires by thermal transformation of calcium dodecyl sulfate in
EG or N,N-dimethylformamide (DMF) at 100 °C for 15 min.
Two samples were prepared both in EG solution at 100 °C
with different heating methods. When microwave heating was
used, it took only 15 min for the formation of CaSO4·0.5H2O
nanowires. In comparison, much longer time (60 h) was
needed for the formation of CaSO4·0.5H2O nanowires using oil
bath heating. These results indicate that the microwave heating
could remarkably shorten the reaction time as compared to the
conventional heating method. It was found that different types
of organic solvents (EG or DMF) had no obvious influences on
the crystal phase, morphology, and formation time of the
product.
Tipcompor et al.622 synthesized SrCO3 and BaCO3 nano-
particles using Sr(NO3)2 or Ba(NO3)2 and Na2CO3 in EG
under cyclic microwave irradiation at 20% of 180 W for 20 min;
the as-prepared orthorhombic SrCO3 and BaCO3 nanoparticles
had particle sizes of 20−50 and 40−100 nm, respectively. Ma et
al.392 synthesized SrCO3 with an olive-like morphology using
Sr(NO3)2 and (NH4)2CO3 in EG by a microwave-assisted
process at 90 °C for 5 min. They also prepared BaCO3
nanorods using Ba(NO3)2 and (NH4)2CO3 in the presence
of NaOH or HMTA in EG by the microwave-assisted method
at 90 °C. The microwave heating time and type of alkali played
important roles in the size and morphology of BaCO3. BaCO3
nanorods assembled from nanoparticles were obtained in the
presence of a strong alkali NaOH in EG by microwave heating
at 90 °C for 40 min; however, BaCO3 nanorods with a
hexagonal cross section formed in the presence of a weak
alkalescent additive.623
Muraliganth et al.625 reported the microwave-polyol syn-
thesis of Li2FeSiO4 and Li2MnSiO4 nanoparticles using
tetraethyl orthosilicate, LiOH, and Fe(CH3COO)2 or Mn-
(CH3COO)2 or Mn(CH3COO)2·4H2O in tetraethylene glycol
at 300 °C for 5 min. Phuruangrat et al.626 synthesized CdMoO4
nanoparticles with sizes of 14−20 nm using Cd(NO3)2·4H2O
and Na2MoO4·2H2O in propylene glycol by microwave heating
at 20% microwave power of 180−600 W for 20−60 min;
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however, the product consisted of aggregated CdMoO4
nanopartcles. CaWO4 nanoparticles with an average particle
size of 12 nm were synthesized using Ca(NO3)2 and Na2WO4
in EG via microwave irradiation.627
3.5. Nanocomposites
Microwave-based methods have been employed to synthesize
inorganic nanostructures on various substrates. The effects of
microwaves on heterogeneous systems have also been
investigated both experimentally and theoretically. The
proposed mechanism is the rapid heating of the high dielectric
loss solvent leading to the formation of nanostructures on the
substrate. However, the exact reason why the nanostructures
form on the substrate and not homogeneously in the solution
phase has not been fully understood. Anumol et al.628 proposed
a formation mechanism for metal nanoparticles on substrates.
They discussed the thermodynamic and kinetic aspects of
reduction of metal salts by EG under microwave heating
conditions. They discussed the temperatures above which the
reduction of the metal salt is thermodynamically favorable and
temperatures above which the rates of homogeneous nucleation
of the metal and the heterogeneous nucleation of the metal on
supports are favored. They investigated different conditions
that favor the heterogeneous nucleation of the metal on the
supports over homogeneous nucleation in the solvent based on
the dielectric loss parameters of the solvent and the support
and the metal/solvent and metal/support interfacial energies.
They showed that metal particles can be selectively formed on
the substrate even under situations where the temperature of
the substrate is lower than that of the surrounding medium.
Many kinds of nanocomposites have been prepared by the
microwave-assisted polyol method, including Au/Ag,629−631
Ag/Ni,632 Pt/C,633−640 Pt/graphene,641,642 Pt/carbon nano-
tubes,643−645 Pd/carbon nanotubes,646 Ni/carbon nano-
tubes,647,648 PtPd/C,649 PtSn/C,650 PtRu/C,638,651 PtAuSn/
C, 652 PtRuIr/C, 653 Pt 75 Co 25 /C, 654 Pt 70 Pd 20 Co 10 /C, 654
Pt 50 Pd 30 Co 20 /C, 654 PtRuNi/C, 655 PtRu/carbon nano-
tubes,656,657 PtSn/carbon nanotubes,658,659 PtFe/carbon nano-
tubes,660 PtZn/carbon nanotubes,661 CoNi/carbon nano-
tubes,662 SnO2/C,663 MnO/C,664 Fe3O4/graphene,665 Fe3O4/
carbon nanotubes,666 Bi2Te3/carbon nanotubes,667 Ru/MgO/
carbon nanotubes,668 Pt−S-SnO2/carbon nanotubes,669 Ru/γ-
Al2O3,670 Ag/TiO2,671 Bi/Bi2O3,672 Ag/SiO2,673 C/ZnO,674 C/
MnO,675 AgCl/Ag,676 Sb-doped PbTe/Ag2Te,677 Ag/poly-
carbazole,678 metal (Pt, Ag or Cu)/polyacrylamide,470 metal
(Pd or Ag)/polyacrylonitrile,679 Fe3O4/polyacid,680 Fe3O4/
polypyrrole,557 and metal sulfide (Ag2S, Cu2S, or HgS)/
polyacrylamide.471
Tsuji et al.629 investigated the role of Cl− ions in the
formation of Au/Ag core−shell nanostructures through a two-
step microwave-polyol process in the solvent of EG. In the
absence of Cl− ions, the major product consisted of spherical
Ag nanoparticles, and few Au/Ag nanoparticles could be
produced. However, higher Cl− ion concentration led to the
formation of a significant amount of AgCl. A small amount of
Cl− anions (∼0.3 mM) was found to be a key factor for the
preferential formation of Au/Ag core−shell nanostructures with
well-defined shapes. The role of Cl− anions was discussed in
terms of shape-selective oxidative etching of spherical Ag
nanoparticles and the formation of AgCl, leading to slow face-
selective crystal growth by decreasing the concentration of free
Ag+ ions. They also prepared shape-dependent Au/Ag core−
shell nanostructures by using a two-step method. First, Au
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nanocrystal seeds with various shapes including single-crystal
octahedron, single-twinned triangle or hexagon plate, and
multiple-twinned decahedron were prepared by reducing
HAuCl4 in EG in the presence of PVP by microwave heating.
Subsequently, Au seeds were added into DMF solution
containing AgNO3 for the growth of Ag shells by oil bath
heating. The shape of Ag shells strongly depended on the shape
of initiated Au seeds. These newly produced triangular or
hexagonal platelike, octahedral, and multiple-twinned decahe-
dral Au/Ag nanostructures were mainly dominated by Ag shells
having the (111) facet. These studies indicate that it is possible
to controll the core−shell nanostructures with desirable crystal
planes by using the same seeds in the appropriate solvent.630
They also prepared octahedral and decahedral Au/Ag core−
shell nanocrystals in high yields using a two-step reduction
method. In the first step, octahedral or decahedral Au core
seeds were prepared by reducing HAuCl4·4H2O in tetra-
ethylene glycol by microwave heating or in diethylene glycol by
oil bath heating, respectively, in the presence of PVP. In the
second step, Ag shells were grown on Au seeds in DMF in the
presence of PVP by oil bath for 3 h or microwave heating for 10
min. Octahedral or decahedral Au/Ag nanocrystals nearly fully
covered by uniform Ag shells were prepared by oil bath heating.
In contrast, decahedral Au/Ag core−shell particles formed
through stepwise growth of tetrahedral units after covering
decahedral Au cores with thin Ag shells by fast microwave
heating.631
Tsuji et al.632 prepared Ag core/Ni shell nanoparticles in
high yield by reduction of a mixture of AgNO3 and NiSO4·
6H2O or NiCl2·6H2O or Ni(NO3)2·6H2O in EG in the
presence of NaOH and PVP by microwave heating at 400 W
for 10 min. Nanoparticles with average sizes of 36 ± 6, 22 ± 3,
and 33 ± 4 nm were obtained from NiSO4·6H2O, NiCl2·6H2O,
and Ni(NO3)2·6H2O, respectively. The Ag/Ni core−shell
nanostructures were confirmed by the contrast of TEM−
energy dispersed X-ray spectroscopy (EDS) measurements in
Figure 18. The distributions of Ag and Ni components along
the cross-section line of a typical nanoparticle shown in Figure
18c and similar line analysis indicated that Ni shells with
different thicknesses were grown on spherical Ag cores. The
Figure 18. TEM image and EDS data of Ag core/Ni shell
nanoparticles obtained from a mixture of AgNO3 and Ni(NO3)2·
6H2O by microwave heating. Reprinted with permission from ref 632.
Copyright 2010 Elsevier B.V.
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structure and Ag/Ni atomic ratio of the product were
essentially independent of the nickel salt. Although Ag/Ni
nanoparticles could be prepared by the oil bath heating, it took
at least 40 min, and the average size of Ag/Ni nanoparticles and
thicknesses of Ni shells were 57 ± 17 and 17 ± 2.3 nm,
respectively, which were larger than those obtained by
microwave heating. These results indicate that smaller nano-
particles with a narrower size distribution can be prepared in a
shorter time under microwave irradiation as compared to those
obtained by the conventional heating. The growth mechanism
of Ag/Ni nanoparticles was also proposed.
Song et al.634 prepared Pt/C nanocomposites with various Pt
contents using H2PtCl6 and NaOH in EG (pH > 10) in the
presence of commercial carbon black by the pulsed microwave-
assisted polyol method. Pt nanoparticles were highly dispersed
on the carbon support and had a narrow particle size
distribution with a mean particle size of ∼2.7 nm. Hu et
al.635 prepared Pt/C and Pt−Ir/C nanocomposites with
different atomic ratios using commercial carbon black,
H2PtCl6·6H2O, and H2IrCl6·6H2O in EG in a closed vessel
by a microwave-assisted polyol process at 190 °C for 30 min.
The average Pt−Ir particle size only changed slightly, and the
crystalline structure gradually became more amorphous with
increasing Ir content. The particle size could be controlled by
altering the pH value of solution and microwave heating rate.
As compared to the microwave-polyol process in an open
vessel, the microwave heating process in a closed vessel could
attain a very fast heating rate, resulting in highly dispersed Pt/C
and Pt−Ir/C nanoparticles. Highly dispersed Pt nanoparticles
on mesoporous carbon nanofibers were prepared using
H2PtCl6, NaOH, and preformed ordered mesoporous carbon
nanofibers or ordered mesoporous carbon as the support in EG
by the microwave-polyol method.636,637 Guo et al.639 prepared
the Pt/carbon aerogel nanocomposite using H2PtCl6·6H2O and
KOH in the presence of carbon aerogel powder in EG by a
microwave-assisted polyol process at 800 W for 3 min.
Spherical Pt nanoparticles with a mean size of 2.7 nm were
well dispersed on the carbon aerogel. The Pt/carbon aerogel
catalyst showed higher electrochemical catalytic activity for
methanol oxidation than that of a commercial Pt/C catalyst
with the same Pt loading. Lebègue et al.640 reported the
microwave-polyol preparation of the Pt/C nanocomposite
using H2PtCl6·6H2O (pH value was adjusted to 11 by using 1
M NaOH solution) in EG. Pt/C nanocomposite prepared by
the pulsed microwave polyol method displayed higher active
surface areas and better kinetic parameters toward oxygen
reduction reaction than those of a Pt/C catalyst prepared by
the conventional polyol refluxing. The Pt/C nanocomposite
synthesized by pulsed microwave heating had a mean particle
size of ∼2.5 nm against ∼3.0 nm for that prepared by the
conventional heating. Sarkar et al.654 prepared carbon-
supported Pt75Co25, Pt70Pd20Co10, and Pt50Pd30Co20 alloy
nanoparticles with 20 wt % metal loading using H2PtCl6·
6H2O, (NH4)2PdCl4, CoCl2·6H2O, and NaOH in tetraethylene
glycol in the presence of carbon black by a microwave-assisted
solvothermal process at 300 °C for 15 min.
Xu et al.643 prepared the nanocomposite of Pt nanoparticles
(15 ± 3 nm) dispersed on carbon nanotubes using H2PtCl6·
6H2O, KOH, and commercial carbon nanotubes in EG under
microwave irradiation at 800 W for 1 min. Sakthivel et al.644
deposited Pt nanoparticles on multiwalled carbon nanotubes
with a high loading using H2PtCl6, NaOH, a zwitterionic
surfactant (3-(N,N-dimethyldodecylammonio) propanesulfo-
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nate), and multiwalled carbon nanotubes in EG by the
microwave-assisted polyol method. The heating time and
temperature were found to be the key factors for depositing Pt
nanoparticles homogeneously on carbon nanotubes, and the
smallest average particle diameter of 1.8 nm was obtained
through microwave heating to 140 °C for 50 s. Pt nanoparticles
with sizes less than 7 nm deposited on preformed carbon
nanotubes were prepared using H2PtCl6 in EG in the presence
of SDS by a microwave-polyol process at 150 °C for 20 min.645
Hsieh et al.646 deposited Pd nanoparticles on multiwalled
carbon nanotubes by microwave heating an EG solution of
PdCl2 and KOH with a household microwave oven at a
microwave power of 720 W for 3 min. Ni nanoparticles
supported on carbon nanotubes were prepared using NiCl2,
NaOH, Na2CO3, N2H4·H2O, and preformed carbon nanotubes
in EG by microwave heating for 1 min.648 The microwave-
assisted polyol method was adopted for the preparation of the
Ru/MgO/carbon nanotube nanocomposite using RuCl3·nH2O
(n = 1−3) and preformed MgO and carbon nanotubes in EG
under microwave irradiation for 1 min, and Ru nanoparticles
with sizes of 1.3−2.0 nm were uniformly dispersed on MgO
and carbon nanotubes.668
The metal/metal oxide nanocomposites have also been
prepared by the microwave-assisted polyol method. Okal et
al.670 prepared the Ru/γ-Al2O3 nanocomposite containing 1.1%
Ru nanoparticles by reduction of RuCl3 in EG using the
microwave-assisted solvothermal method at 200 °C for 20 min.
The microwave-assisted polyol synthesis of the Ag/TiO2
nanocomposite was also reported.671 Bi/Bi2O3 composite
microspheres were synthesized via a microwave-assisted
solvothermal route for 2.5 min, in which BiCl3 was used as
the bismuth source, glucose as a reductant, and EG as the
solvent.672
The microwave-assisted polyol method has also been
adopted for the rapid synthesis of nanocomposites containing
metal alloy nanostructures. Wang et al.656 prepared the
nanocomposite of Pt−Ru nanoparticles/multiwalled carbon
nanotubes using H2PtCl6, RuCl3, and preformed 1-amino-
pyrene-functionalized multiwalled carbon nanotubes in EG by
the microwave-polyol method for 2 min. Polyoxometallate-
stabilized Pt−Ru alloy nanoparticles supported on multiwalled
carbon nanotubes were synthesized by microwave heating an
EG solution of H3PMo12O40, H2PtCl6·6H2O, RuCl3·xH2O, and
KOH in the presence of multiwalled carbon nanotubes.657 The
microwave-assisted polyol method was also applied to the
preparation of Pt−Sn alloy nanoparticles immobilized on
carbon nanotubes and nitrogen-doped carbon nanotubes.658,659
The nanocomposite of Pt−Fe nanoparticles/carbon nanotubes
was prepared by the microwave-polyol method. By adjusting
the experimental parameters, the ratio of Fe/Pt and the
attached density of PtFe nanoparticles on the surface of carbon
nanotubes could be varied.660 Hsieh et al.661 prepared Pt−Zn
nanoparticles with sizes of ∼3−5 nm dispersed on carbon
nanotubes by the microwave-assisted polyol method. The
reaction system was composed of PtCl4, Zn(NO3)2, KOH, and
EG in the presence of preformed carbon nanotubes, which was
heated for a total time of 6 min in a household microwave oven
with a power of 720 W. Wu et al.662 prepared Co−Ni alloy
nanoparticles with average diameters in the range of 15−48 nm
deposited on the preformed multiwalled carbon nanotubes by
the microwave-assisted method at 600 W for 2 min, and
Co(CH 3 COO) 2 ·4H 2 O, Ni(CH 3 COO) 2 ·4H 2 O, a small
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amounts of NaOH and hydrazine hydrate were used as the
reactants in EG.
The microwave-assisted polyol synthesis of nanocomposites
containing metal oxide and carbon has also been reported.
Chen et al.666 prepared the nanocomposite of Fe3O4 nano-
particles (3−5 nm)/multiwalled carbon nanotubes by in situ
decomposition of iron(III) acetylacetonate in polyol under
microwave irradiation at 200 °C for 15 min. The resulting
nanocomposite showed a superparamagnetic property at room
temperature and was stable in aqueous dispersion for 2 months.
Sulfated SnO2 modified multiwalled carbon nanotube nano-
composite as the support for Pt nanoparticles (Pt−S−SnO2/
carbon nanotubes) was synthesized by a combination of the
sol−gel and pulsed microwave polyol method.669 Guo et al.674
reported the deposition of carbon on the surface of ZnO
nanorods by the microwave-assisted polyol method. The
surface of the preformed ZnO nanorods was first modified by
amino groups and then grafted by glucose, and finally irradiated
by microwaves to induce the transformation of glucose into
carbon in glycerol at 100 °C for 30 min. Courtel et al.663
prepared SnO2 nanoparticles (5−10 nm)/carbon nanocompo-
sites using SnCl2·2H2O in the presence of a carbon matrix in
the solvent of EG by the microwave-assisted polyol refluxing at
190−195 °C for 1 h. They also investigated the effect of the
heating method and found that the use of microwaves was
beneficial for not only shortening the reaction time but also
producing smaller SnO2 nanoparticles that were also better
dispersed within the carbon matrix.
As compared to the preparation of the nanocomposites
containing metal or metal oxide nanoparticles, the synthesis of
the nanocomposites composed of nanostructured metal
telluride is much more difficult and complex, and the related
work has been less reported in the literature. Dong et al.677
reported the microwave-assisted solvothermal preparation of
Sb-doped PbTe/Ag2Te core−shell composite nanocubes with
the core of well-crystallized cubic Sb-doped PbTe and the shell
of amorphous Ag2Te. In this method, SbCl3, AgNO3,
Pb(CH3COO)2·3H2O, Na2TeO3, NaOH, and NaBH4 were
used as the reactants, and EG was used as the solvent by
microwave heating at 250 °C for 20 min. The TEM
micrographs of Sb-doped PbTe/Ag2Te core−shell composite
nanocubes are shown in Figure 19. The product consisted of
nanocubes with edge lengths of 25−55 nm, and the nanocube
was composed of a well-crystallized inner nanocube as a core
with edge lengths of 20−50 nm and an amorphous outer shell
with thicknesses of 3−6 nm. The selected-area electron
diffraction (SAED) pattern taken from the central site of a
single nanocube revealed that the core of the nanocube was a
well-crystallized single crystal, and the diffraction spots (Figure
19c) could be assigned to the Sb-doped PbTe crystal with a
cubic structure. The high-resolution TEM image in Figure 19d
provides further insight into the detail of the core/shell
nanocube, which shows that the core was highly crystalline with
a d-spacing of lattice fringes of 0.3220 nm; this value is in
agreement with the calculated d(200) value of the cubic Sb-
doped PbTe. The reaction mechanism of Sb-doped PbTe/
Ag2Te core/shell composite nanocubes was proposed.677
The control over the particle size, size distribution, and
dispersity is very important for the synthesis and application of
high-performance inorganic/organic nanocomposites. It is
desirable to develop simple, fast, and low-cost methods for
the synthesis of inorganic/organic nanocomposites. Zhu et
al.470 have developed a novel single-step microwave-assisted
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Figure 19. Characterization of Sb-doped PbTe/Ag2Te core/shell
composite nanocubes prepared by the microwave-assisted polyol
solvothermal method at 250 °C for 20 min. (a and b) TEM
micrographs; (c) SAED pattern taken from the core of a single
nanocube; and (d) HRTEM image of a single nanocube. Reprinted
with permission from ref 677. Copyright 2012 Elsevier B.V.
polyol method for the rapid synthesis of inorganic/organic
nanocomposites. They prepared polyacrylamide (PAM)/metal
(M = Pt, Ag, Cu) nanocomposites with metal nanoparticles
homogeneously dispersed in the polymer matrix using the
corresponding metal salt and acrylamide monomer in EG by
the rapid microwave-assisted polyol method. This method is
based on the single-step simultaneous formation of metal
nanoparticles and polymerization of acrylamide monomer in
solution, leading to the homogeneous distribution of metal
nanoparticles in the polyacrylamide matrix. EG acts as a solvent,
reducing reagent, and microwave absorber; thus no additional
reductant is needed. Another advantage of this method is that
no initiator for acrylamide polymerization and no surfactant for
stabilization of metal nanoparticles are necessary. This makes it
possible to avoid subsequent complicated work-up procedures
for removal of the additives, leading to rapidity, simplicity, and
low-cost for the preparation of polymer/metal nanocomposites.
The diameters of Ag nanoparticles in the PAM/Ag nano-
composite were in the range of 6−18 nm with an average
diameter of 11.3 ± 1.9 nm prepared by microwave heating an
EG solution containing 0.01 M AgNO3 and 3 M acrylamide at
125 °C for 15 min. As compared to pure PAM, the thermal
stability of the PAM/Ag nanocomposite was improved. This
novel single-step microwave-assisted polyol method can be
extended to synthesize other inorganic/organic nanocompo-
sites.
Zhu et al.471 synthesized polyacrylamide/metal sulfide (Ag2S,
Cu2S, HgS) nanocomposites with metal sulfide nanoparticles
homogeneously dispersed in the polyacrylamide matrix using
corresponding metal salt, S powder, and acrylamide monomer
in EG by microwave heating at 125 or 190 °C for 15−60 min.
This method is based on the simultaneous formation of metal
sulfide nanoparticles and polymerization of the acrylamide in
the same reaction system, leading to a homogeneous
distribution of metal sulfide nanoparticles in the polyacrylamide
matrix without aggregation. EG acts simultaneously as a
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Chemical Reviews Review

Figure 20. (a) TEM micrograph of the PAM/Ag2S nanocomposite prepared by microwave heating an EG (50 mL) solution containing 2 mmol of
AgNO3, 2 mmol of S, and 0.15 mol of acrylamide at 125 °C for 15 min, the SAED pattern of an individual Ag2S nanoparticle (upper inset), and
magnified TEM micrograph of an individual nanoparticle (lower inset); (b) HRTEM image of the edge of an individual Ag2S nanoparticle (inset:
fast Fourier transform (FFT) pattern of the image). Reprinted with permission from ref 471. Copyright 2007 American Chemical Society.

solvent, microwave absorber, and reductant; thus no additional
reductant is needed. Another advantage of this method is that
no initiator for acrylamide polymerization and no surfactant for
the stabilization of metal sulfide nanoparticles are necessary.
Figure 20a shows the TEM micrograph of the PAM/Ag2S
nanocomposite prepared by the rapid microwave-assisted
polyol method, from which one can see that spherical Ag2S
nanocrystals were homogeneously dispersed in the PAM
matrix. The insets of Figure 20a and b show that each Ag2S
nanocrystal was single-crystalline in structure. The diameters of
Ag2S nanocrystals were in the range of 36−54 nm, and the
average diameter of Ag2S nanocrystals was 43.8 ± 1.7 nm. The
PAM/Ag2S nanocomposite with larger Ag2S average size and
broader size distribution was obtained by microwave heating at
125 °C for a longer reaction time (1 h) or at a higher
temperature (190 °C) for 15 min. As compared to pure
polyacrylamide, the thermal stability of Ag2S/polyacrylamide
and Cu2S/polyacrylamide nanocomposites was improved.471
conducting fluids (electrolytes) and uses in electric battery. The
most commonly studied systems contain ammonium, phos-
phonium, pyridinium, or imidazolium cations, with varying
heteroatom functionality. Common anions that yield ionic
liquids include hexafluorophosphate [PF6]−, tetrafluoroborate
[BF4]−, and chloride CI−. Ionic liquids are a new family of
environmentally friendly solvents in terms of immeasurable
vapor pressure, which are promising for green chemical
reactions and materials synthesis. The detailed discussion on
the properties and applications of ionic liquids has been
provided in a book entitled “Ionic Liquids as Green
Solvents”.682 The example of the industrial application of
ionic liquids has been reported, and others may not be far
behind.683
The chemical structures of some typical ionic liquids used in
the microwave-assisted preparation of inorganic nanostructures
are as follows:

4. MICROWAVE-ASSISTED PREPARATION OF
NANOSTRUCTURES USING IONIC LIQUIDS
4.1. Ionic Liquids and Microwave Heating Effects
Solvents are very important for microwave-assisted synthesis. 1-methyl-3-(3-carboxyethyl)-imidazolium tetrafluoroborate
The most commonly used solvents for chemical reactions and [EmimCO2H][BF4]
materials synthesis are water and organic solvents. Water is
widely available, cheap, nonflammable, nontoxic, and environ-
mentally benign. However, the liquid state temperature range
of water is narrow (0−100 °C), and many organic compounds
have low solubilities in water. These disadvantages limit the
applications of water as a solvent for materials synthesis. 1-n-butyl-3-methylimidazolium tetrafluoroborate [BMIM]-
Organic solvents have rich diversity in category and properties; [BF4]
however, many organic solvents have low boiling points and
high vapor pressures, and the solubilities of inorganic reactants
in organic solvents are usually low. Some organic solvents are
highly toxic, flammable, and even explosive. In particular, the
high vapor pressure and toxicity of some volatile organic
solvents may cause significant environmental problems.681
The term “ionic liquid” is used loosely to describe organic N-butylpyridinium tetrafluoroborate
salts that melt below about 100 °C and have an wide liquid In recent years, ionic liquids have been paid much attention
temperature range. Ionic liquids define a class of fluids rather as the novel green media for the synthesis of inorganic
than a small group of individual examples. Ionic liquids have materials.681,684,685 The importance of ionic liquids in the field
many applications, such as green solvents and electrically of inorganic materials synthesis has been realized in terms of
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Chemical Reviews
their excellent properties such as high thermal stability,
immeasurable vapor pressure, wide temperature range for
liquid state, low interfacial tension, and high ionic conductivity,
while these properties are dependent on their structures and
combination of ionic components. Ionic liquids are highly
susceptible to microwave irradiation because of their ionic
character and high polarizability; thus, they are excellent
microwave adsorbers.
The combination of microwave heating and ionic liquids
provides superior benefits for the rapid synthesis of materials
over the conventional heating methods, especially in terms of
rapidness and energy saving. With the help of ionic liquids, the
microwave-assisted rapid synthesis of nanostructured materials
can be realized even in the nonpolar solvent, which does not
adsorb microwaves. Leadbeater et al.57 investigated the use of
an ionic liquid as an aid for microwave heating of nonpolar
solvents. They found that the addition of a small quantity of an
ionic liquid to a nonpolar solvent greatly increased the rate and
yield of chemical reactions. By adding a small amount of 1,3-
dialkylimidazolium iodide in hexane, the temperature reached
217 °C after microwave heating at 200 W for 10 s; in
comparison, the temperature was only 46 °C after microwave
heating at 200 W for 10 s in the absence of the ionic liquid.
In 2004, Zhu et al.685 have reported their pioneering work on
the microwave-assisted ionic liquid (MAIL) method for the
rapid controlled preparation of Te nanorods and nanowires by
combining the advantages of both the ionic liquid and
microwave heating. The TEM characterization of the typical
samples is shown in Figure 21. Figure 21a and b shows TEM
Figure 21. TEM micrographs of two typical samples prepared by the
microwave-assisted ionic liquid method. (a)−(c) Te nanorods; (d)
electron diffraction pattern of a single Te nanorod; (e) HRTEM image
of a single Te nanorod; and (f) Te nanowires. Reprinted with
permission from ref 685. Copyright 2004 Wiley-VCH.
micrographs of the as-prepared Te nanorods with diameters
mostly ranging from ∼15 to ∼40 nm, and with aspect ratios of
most nanorods in the range from 10 to 20. Figure 21c shows a
single Te nanorod with a diameter of 32 nm and a length of
610 nm; its corresponding electron diffraction pattern is shown
in Figure 21d. Electron diffraction patterns on different
nanorods or different positions of a given single nanorod
were essentially the same, indicating that the nanorod was
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single-crystalline in structure. Figure 21e shows the HRTEM
micrograph of the same single nanorod, which shows that the
nanorod was structurally single-crystalline with the periodic
fringe spacing of 0.5927 nm along the longitudinal axis of the
nanorod that corresponds to the interplanar spacing between
the (001) planes of the hexagonal Te. Te nanorods had the
preferential growth direction along the [001] zone axis. By
controlling the experimental parameters, exclusive Te nano-
wires or nanorods could be produced. Figure 21f shows a TEM
micrograph of Te nanowires. Most of these nanowires had
diameters ranging from 20 to 100 nm with lengths of tens of
micrometers. They have demonstrated that the microwave-
assisted ionic liquid method is a fast, high-yield, and
environmentally friendly route for the production of inorganic
nanostructures.
The microwave-assisted ionic liquid method has been proven
to be suitable for the rapid synthesis of a variety of elemental
and compound nanostructures, including Au,686−688 Co,689,690
Mn,689,690 Cr,690 Mo,690 W,690 Re,690 Ru,690 Os,690 Rh,690 Ir,690
Gd4F3,691 Te,685 C,692 ZnO,693−695 Fe2O3,696−698 Fe3O4,698,699
FeOOH,698 SnO2,700 In2O3:Sn,701 CuO,697,702−705 MnO2,706
Mn3O4,697 3PbO·H2O,697 PbO,697 TiO2,707,708 CeO2,709
ZnFe2O4,710 PbCrO4,711 Pb2CrO5,711 MgF2,712 CaF2,712
SrF2,696,712 FeF2,696 CoF2,696 ZnF2,696 REF3 (RE = La−Lu,
Y),696,713−715 NaYF4,716 Zn(OH)F,717−719 β-Co(OH)2,697 β-
Ni(OH)2,697 Cd(OH)2,697 La(OH)3,697 ZnS,720,721 CdS,721
Bi 2 S 3 , 722 Sb 2 S 3 , 722 Bi 2 Se 3 , 723 Bi 2 Te 3 , 724 CdTe, 725 La-
PO4:Ce,Tb,726,727 NH4Fe2(PO4)2OH·2H2O,728 CoC2O4,729
Cu/C,730 Ni/C,730 Pt/carbon nanotubes,731 Rh/carbon nano-
tubes,731 Pt−Ru/carbon nanotubes,732 Ru/graphene,733 Rh/
graphene,733 and cellulose/calcium silicate.734
4.2. Metals, Semimetals, Nonmetals, and Alloys
Much effort has been devoted to the microwave-assisted rapid
preparation of a variety of metal nanostructures using an ionic
liquid. Redel et al.686 prepared Au nanoparticles by thermal,
photolytic, or microwave-assisted decomposition/reduction
under argon from Au(CO)Cl or KAuCl4 in the presence of
n-butylimidazole dispersed in the ionic liquid [BMIm]+[BF4]−,
[BMIm]+[OTf]−, or [BtMA]+[NTf2]− ([BMIm]+ = n-butyl-
methylimidazolium, [BtMA]+ = n-butyltrimethylammonium,
[OTf]− = −O3SCF3, [NTf2]− = −N(O2SCF3)2). Uniform
nanoparticles of ∼1−2 nm in diameter were produced in
[BMIm]+[BF4]− and increased in size with the molecular
volume of the ionic liquid anion. Li et al.735 prepared Au
nanosheets using HAuCl4 in an ionic liquid 1-butyl-3-
methylimidazolium tetrafluoroborate ([BMIM][BF4]) by mi-
crowave heating, and it was found that the ionic liquid could act
as the template for the formation of Au nanosheets. Ren et
al.687 produced Au nanostructures and microstructures such as
polyhedral crystals, single-crystalline nanoplates, hollow trapezi-
form crystals, holey polyhedra, and dendrites using HAuCl4·
4H2O in a variety of imidazolium- and pyridinium-based ionic
liquids as the solvents without the addition of any capping
agent or additional reducing agent via microwave heating. The
influence of the ionic liquid anions and cations on the topology
(size, shape, etc.) of the product was investigated. It was found
that the anions of the ionic liquids controlled the topology of
the product, whereas the cations of the ionic liquids had less
influence. The HAuCl4 concentration, reaction temperature,
and heating method were key factors for the topological
structures of the product. The thickness of single-crystalline
nanoplates could be adjusted from 16 to 320 nm by varying the
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HAuCl4 concentration and reaction temperature. Octahedral
Au nanocrystals were also fabricated in an alcohol ionic liquid
by the microwave-assisted ionic liquid method in the absence of
any extra capping agent. This method is based on a chemical
reaction of HAuCl4·4H2O in 1-(3-hydroxylpropyl)-3-methyl-
imidazolium tetrafluoroborate ([C3OHmim][BF4]). Upon
adjusting the HAuCl4·4H2O concentration and reaction
temperature, Au nanoplates and micrometer-sized particles
were obtained.688
Marquardt et al.689 adopted the microwave-assisted ionic
liquid method for the preparation of Co and Mn nanoparticles
by decomposition of metal carbonyls of Co2(CO)8 and
Mn2(CO)10, respectively, in the functionalized ionic liquid 1-
methyl-3-(3-carboxyethyl)-imidazolium tetrafluoroborate
[EmimCO2H][BF4]. The sizes of Co and Mn nanoparticles
were 1.6 ± 0.3 and 4.3 ± 1.0 nm, respectively. In comparison,
the sizes of Co and Mn nanoparticles produced in the
nonfunctionalized ionic liquid [BMIM][BF4] were larger (5.1
± 0.9 and 28.6 ± 11.5 nm, respectively). The as-prepared
metallic nanoparticles were stable in the absence of capping
ligands (surfactants) for more than 6 months, although the
particle sizes were slightly changed. Vollmer et al.690 prepared a
variety of transition-metal nanoparticles of Cr, Mo, W, Mn, Re,
Ru, Os, Co, Rh, and Ir by a rapid (3 min) and energy saving
(10 W) microwave irradiation under argon atmosphere from
metal−carbonyl precursors [Mx(CO)y] in the ionic liquid
[BMIM][BF4]. Most of the as-prepared metallic nanoparticles
had sizes of ∼0.8−5 nm. The microwave preparation was
compared to UV irradiation (1000 W, 15 min) or conventional
thermal decomposition (180−250 °C, 6−12 h) of [Mx(CO)y]
in the ionic liquid, and the metallic nanoparticles obtained by
the microwave heating had smaller (<5 nm) and more uniform
sizes.
Zhu et al.685 have developed the microwave-assisted ionic
liquid method for the rapid synthesis of Te nanorods and
nanowires in the ionic liquid of N-butylpyridinium tetrafluor-
oborate. By controlling experimental parameters, exclusively Te
nanorods or Te nanowires were obtained. Their experiments
showed that both the ionic liquid and microwave heating
played important roles in the formation of Te nanorods and
nanowires.685 Safavi et al.692 prepared carbon nanodots with an
average size of ∼6 nm via the microwave-assisted ionic liquid
method. In this method, a desired amount of water-immiscible
ionic liquid N-octylpyridinium hexafluorophosphate was heated
in a microwave oven (450 W) for ∼2 min. The ionic liquid
acted not only as an excellent medium for absorbing
microwaves, but also as a carbon source.
4.3. Metal Oxides
In the microwave-assisted ionic liquid synthesis of metal oxide
nanostructures, a metal compound is used as the metal source,
an alkaline reagent is usually used to provide an alkaline
environment, and an additive or a surfactant is sometimes
adopted to control the morphology and size of the product.
Nanostructures of metal oxides with various morphologies have
been prepared in the presence of an ionic liquid by microwave
heating, and some examples will be discussed below.
Wang et al.693 synthesized ZnO structures with flower-like
and needle-like shapes by the simple microwave-assisted
approach using an ionic liquid [BMIM][BF4]. Both the ionic
liquid and microwave heating played important roles in the
formation of different morphologies of ZnO. By controlling
experimental conditions, exclusive ZnO needles or flowers
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could be synthesized at a temperature of 50, 90, or 125 °C in a
short period of time (5 or 10 min). Flower-like ZnO nanosheet
aggregates were prepared by microwave heating in an ionic
liquid of 1-(2-hydroxylethyl)-3-methylimidazolium chloride.694
Nanoparticle-constructed microspheres, plate-constructed
stacks, rod-constructed flower-like structures, and complex
ZnO aggregates were synthesized using Zn(CH3COO)2·2H2O
and an ionic liquid hydrate tetrabutylammonium hydroxide
(N(C4H9)4OH·30H2O) by microwave heating for 1 min. In
this synthesis, the ionic liquid had multifunctions (solvent,
absorber of microwaves, reactant, and template).695
Wang et al.702 prepared CuO nanowhiskers using CuCl2·
2H2O and NaOH in the presence of an ionic liquid
[BMIM][BF4] by the rapid microwave-assisted ionic liquid
approach at 80 °C. It was found that the ionic liquid
[BMIM][BF4] had a significant influence on the morphology
of CuO. CuO nanowhiskers were obtained in the presence of
[BMIM][BF4], while CuO nanosheets were synthesized
without using [BMIM][BF4]. CuO nanostructures with leaf-
like, chrysanthemum-like, and rod-like shapes were prepared
using Cu(CH3COO)2·2H2O and NaOH by the microwave-
assisted approach using an ionic liquid [BMIM][BF4]. By
adjusting the concentration of [BMIM][BF4] and reaction
time, different CuO nanostructures could be obtained in a short
period of time.703 Flower-like and leaf-like CuO nanostructures
were synthesized using CuCl2·2H2O and NaOH in the
presence of an ionic liquid of 1-octyl-3-methylimidazolium
trifluoroacetate by microwave heating at 80 °C for 10 min. By
controlling the concentration of the ionic liquid and reaction
temperature, the morphology of CuO nanostructures could be
adjusted.705
Cao et al.698 reported the microwave-solvothermal ionic
liquid synthesis of a variety of iron oxide nanostructures, such
as α-FeOOH hollow microspheres constructed by self-assembly
of nanoparticles, β-FeOOH architectures, and α-Fe2O3 nano-
particles. It was found that the ionic liquid [BMIM][BF4] had
an influence not only on the crystal phase but also on the
morphology of the product. The effects of the experimental
parameters on the morphology and crystal phase of the product
were studied, and the relationship between the morphology and
crystal phase of the product was discussed. The formation
mechanism of α-FeOOH hollow microspheres was proposed. A
general thermal transformation strategy was designed for the
preparation of α-Fe2O3 hollow microspheres using α-FeOOH
hollow microspheres as the precursor and template, and by
autocatalysis of the adsorbed Fe2+ ions on the α-FeOOH
surface, Fe3O4 hollow microspheres were obtained.698 Li et
al.699 prepared rhombic dodecahedral Fe3O4 nanocrystals via a
rapid microwave-assisted route in the presence of a hydrophilic
ionic liquid N-dodecylpyridinium perchlorate [C12Py]+[ClO4]−,
and the reaction could be completed within 15 min at 90 °C. It
was found that a proper amount of ionic liquid played a key
role in the formation of rhombic dodecahedral Fe 3 O 4
nanocrystals, and the shape of the product could be tuned by
adjusting the experimental parameters. Cao et al.710 reported
the microwave-solvothermal ionic liquid synthesis of ZnFe2O4
nanoparticles using Zn(CH3COO)2·2H2O, Fe(NO3)3·9H2O,
and CO(NH2)2 in the presence of an ionic liquid [BMIM]-
[BF4] at 160 °C for 30 min, and it was found that the ionic
liquid [BMIM][BF4] and microwave heating temperature had
significant effects on the crystal phase of the product.
SnO2 quantum dots with a narrow size distribution (4.27 ±
0.67 nm) were synthesized by microwave-assisted decom-
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position of tin(IV) tert-butoxide (Sn(OtBu)4) in an ionic liquid
[BMIM][BF4] in a 10 mL sealed glass vessel under argon gas
atmosphere at 180 °C for 1 min. The aqueous suspension of
SnO2 quantum dots was used for inkjet printing nanobridges
between gold electrodes on polycarbonate and on silicon chip
as well.700 Bühler et al.701 prepared In2O3:Sn nanoparticles with
an average diameter of 25 ± 3 nm in an ionic liquid
[N(CH3)(C4H9)3][N(SO2CF3)2] by a microwave-assisted
route. Yang et al.706 prepared single-crystalline nanoneedles
and nanorods of cryptomelane-type manganese oxide octahe-
dral molecular sieve (OMS-2) by the microwave-assisted ionic
liquid approach using [BMIM][BF4] at a relatively low
temperature (90 °C) for a short period of time (10 min).
[BMIM][BF4] acted as a cosolvent, structure-directing agent,
and reducing reagent in the reaction system. The multifunc-
tional roles of [BMIM][BF4] simplify the preparation
procedure. On the basis of the redox reaction of MnCl2 and
KMnO4 in the presence of [BMIM]BF4, it was proposed that
the formation of OMS-2 nanoneedles followed the rolling
mechanism with the lamellae as an intermediate. In contrast,
the direct reaction of KMnO4 with [BMIM][BF4] resulted in
the formation of OMS-2 nanorods with diameters as small as
3−6 nm. Wang et al.711 synthesized PbCrO4 rods and Pb2CrO5
with bundle-like and rod-like morphologies adopting reactants
of Pb(CH3COO)2·3H2O, K2Cr2O7, and [BMIM][BF4], with or
without NaOH by the rapid microwave-assisted ionic liquid
method. In the presence of NaOH, Pb2CrO5 bundles and rods
could be synthesized by microwave heating at 90 °C for 10 min.
However, single-crystalline PbCrO4 rods could be obtained by
microwave heating at 50 °C for 10 min in the absence of
NaOH.
4.4. Metal Chalcogenides
The remarkable merit of the microwave-assisted ionic liquid
method for the synthesis of nanostructured metal sulfides is its
rapidness (usually in minutes) as compared to the conventional
heating methods (usually hours or even days), For example,
only 10 min was needed for the microwave-assisted ionic liquid
synthesis of ZnS or CdS nanoparticles using Zn(CH3COO)2·
2H2O or CdCl2·2.5H2O and Na2S·9H2O in the presence of an
ionic liquid [BMIM][BF4] at 100 °C.721 Single-crystalline Bi2S3
and Sb2S3 nanorods were synthesized using the starting
reagents of Bi2O3 or Sb2O3, Na2S2O3, HCl, and EG or
ethanolamine in the presence of an ionic liquid [BMIM][BF4]
by the microwave-assisted ionic liquid method. It was found
that the ionic liquid played an important role in the
morphology of M2S3 (M = Bi, Sb). Bi2S3 nanorods could be
prepared in a short period of time (only 30 s) in the presence
of [BMIM][BF4 ]; however, urchinlike Bi 2S3 structures
consisting of nanorods were obtained without using [BMIM]-
[BF4]. Sb2S3 nanorods were obtained in the presence of
[BMIM][BF4]; however, Sb2S3 nanosheets were obtained in
the absence of [BMIM][BF4].722
Jiang et al.723 synthesized Bi2Se3 nanosheets with thicknesses
of 50−100 nm using Bi(NO3)3·5H2O, Se powder, HNO3,
ethylenediamine, or EG and an ionic liquid [BMIM][BF4] by
microwave heating. It was found that the ionic liquid
[BMIM][BF4] played an important role in the morphology
of Bi2Se3. When ethylenediamine was used, both nanoparticles
and irregularly shaped nanosheets were obtained without using
[BMIM][BF4], while exclusively irregularly shaped nanosheets
formed in the presence of [BMIM][BF4]. When EG was used,
irregularly shaped nanosheets could be obtained in the absence
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of [BMIM][BF4], while hexagonally shaped nanosheets were
formed in the presence of [BMIM][BF4].
Ji et al.724 synthesized Bi2Te3 nanosheets via microwave
heating a reaction system containing Bi(NO3)3·5H2O, Te
powder, KOH, EG, and an ionic liquid of 1-butyl-3-
methylimidazolium bromide. By increasing the amount of the
ionic liquid, a morphology evolution process of Bi2Te3 from a
mixture of nanorods and nanoplates to hexagonally shaped
nanoplates was observed. Hayakawa et al.725 reported the
microwave-assisted ionic liquid synthesis of highly luminescent
thiol-capped CdTe nanocrystals with the zinc blende crystal
structure using CdCl 2 ·2.5H 2 O, H 2 Te gas, and 2-
(dimethylamino)ethanethiol hydrochloride in the presence of
a hydrophobic ionic liquid of 1-methoxymethyl-1-methylpyrro-
lidinium bis(trifluoromethanesulfonyl)amide at 150 °C for
different time periods. The average diameter of CdTe
nanocrystals obtained by microwave irradiation at 150 °C for
80 min was 4.1 nm with a standard deviation of 14%.
4.5. Other Nanostructured Materials
Although some methods have been reported for the
preparation of metal fluorides with diverse morphologies,
either complicated and time-consuming processes or severe
experimental conditions are needed in some methods.
Furthermore, the fluoride reagents used in some methods are
toxic fluorine-containing compounds such as CF3COOH.
Taking the fluorine-containing ionic liquids as examples, the
anion [BF4]− containing ionic liquids such as [BMIM][BF4]
can decompose thermally and hydrolyze under the microwave
heating conditions to release F− ions. Therefore, the ionic
liquids containing the anion of [BF4]− can be used as an
environment-friendly fluorine source for the rapid microwave-
assisted synthesis of nanostructured metal fluorides. On the
basis of this strategy, Xu et al.712 have demonstrated the
microwave-assisted ionic liquid solvothermal method for rapid
synthesis of CaF2 double-shelled hollow microspheres using
Ca(NO3)2·4H2O and NaH2PO4·2H2O in the presence of an
ionic liquid [BMIM][BF4] as the fluorine source at 120 °C for
10 min. This method is simple, time-saving, and environ-
mentally friendly, and can be extended to prepare hollow
microspheres of MgF2 and SrF2. MgF2 hollow microspheres
were prepared with a similar procedure using Mg(NO3)2·6H2O
by microwave heating at 150 °C for 30 min, and SrF2 hollow
microspheres were prepared with a similar procedure using
Sr(NO3)2·4H2O by microwave heating at 120 °C for 10 min.
Jacob et al.696 adopted the microwave-assisted ionic liquid
method for the synthesis of metal fluoride nanostructures such
as FeF2, CoF2, ZnF2, LaF3, YF3, and SrF2 with different
morphologies using an ionic liquid [BMIM][BF4] in a domestic
microwave oven.
Li et al.713 adopted the microwave-assisted ionic liquid
method for the preparation of a series of binary rare earth
fluorides REF 3 (RE = La−Lu, Y) nanostructures and
microstructures using an ionic liquid [BMIM][BF4] as a
solvent, reactant, and template. Lorbeer et al.714 prepared EuF3
nanoparticles using Eu(CH3COO)3·H2O, EG, and an ionic
liquid by microwave heating with a single mode microwave
reactor. Different tetrafluoroborate ionic liquids such as N-
butyl-N-methyl-pyrrolidiniumtetrafluoroborate ([C4mpyr]-
[BF4]), 1-butylpyridinium tetrafluoroborate ([C4py][BF4]), 1-
hexylpyridinium tetrafluoroborate ([C6py][BF4]), (2-hydrox-
yethyl)-trimethylammoniumtetrafluoroborate ([choline]-
[BF 4 ]), trihexyltetradecylphosphoniumtetrafluoroborate
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Figure 22. TEM characterization of Ru nanoparticles (top row) and Rh nanoparticles (bottom row) supported on chemically derived graphene
surface from microwave-assisted decomposition of Ru3(CO)12 and Rh6(CO)16 in an ionic liquid [BMIM][BF4]. Reprinted with permission from ref
733. Copyright 2010 Elsevier Ltd.
([P66614][BF4]), 1-butyl-3-methylimidazoliumhexafluorophos-
phate ([C4mim][PF6]), 1-methyl-3-butylimidazolium chloride
[C4mim]Cl, 1-methyl-3-butylimidazolium tetrafluoroborate
[C4mim][BF4], and tributyltetradecylphosphonium tetrafluor-
oborate [P44414][BF4] were used. The experiments indicated a
strong influence of the ionic liquid on the structure,
morphology, and luminescent properties of the product. The
morphology of the product varied from spherical nanoparticles
to nanorods forming different types of aggregates, such as
bundles, columns, or spherical aggregates. The comparison
experiments were also conducted via the conventional
ionothermal synthesis by heating the reaction mixture at 120
°C for 20 h in a furnace. The microwave synthesis was shown
to be an extremely fast and facile synthesis route, and the
reaction time could be as short as 30 s. In contrast, the
conventional ionothermal synthesis took at least 2 h for a
complete conversion of the starting reactants. In both cases,
nanoparticles with sizes smaller than 15 nm were obtained. The
size and shape of the as-prepared nanostructures varied in
different ionic liquids. They also reported the microwave-
assisted ionic liquid method for the synthesis of GdF3:Eu3+
nanoparticles with particle sizes ranging from 2 to 9.5 nm and
an average size of ∼6 nm using Ln(CH3COO)3·xH2O (Ln =
Gd, Eu) in the ionic liquid [C4mim][BF4]. In this method, the
ionic liquid acted not only as the solvent but also as a fluoride
source.715
Chen et al.716 reported the microwave-assisted ionic liquid
synthesis of NaYF4 spheres formed by self-assembly of
nanoparticles using an ionic liquid [BMIM][BF4] at 200 °C
for 5 min. The diameters of NaYF4 spheres could be tuned by
changing the amounts of the precursors. It was found that the
ionic liquid played key roles such as the solvent, absorbent of
microwaves, and fluorine source for the formation of NaYF4
spheres. Zn(OH)F nanofibers717 and Zn(OH)F nanobelts718
were synthesized under microwave irradiation in the presence
of an ionic liquid of 1,2,3-trimethylimidazolium tetrafluorobo-
rate. Zn(OH)F nanostructures with a flower-like morphology
were prepared using an ionic liquid [BMIM][BF4] via a
microwave-assisted ionic liquid route at 320 W for 5 min; the
flower-like Zn(OH)F had six petals, and every petal was
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composed of lots of acicular nanostructures.719 Pang et al.697
used the structurally similar ionic liquid precursors tetrabuty-
lammonium hydroxide and tetraethylammonium hydroxide for
the synthesis of nanostructures of metal hydroxides including β-
Co(OH)2, β-Ni(OH)2, Cd(OH)2, and La(OH)3 by microwave
heating for 1 min.
Bühler et al.726 prepared LaPO4:Ce,Tb nanoparticles with
sizes of 9−12 nm based on the use of an ionic liquid of
tributylmethylammonium triflylimide [NCH 3 (C 4 H 9 ) 3 ]-
[(SO2CF3)2N] under microwave irradiation at 300 °C for
∼10 s. According to the noncoordinating properties of the ionic
liquid, the phase transfer of LaPO4:Ce,Tb nanoparticles from
polar to nonpolar dispersants was performed. Microwave
heating was extremely fast, resulting in almost instantaneous
crystallization of nanoparticles. Dispersions of LaPO4:Ce,Tb
nanoparticles in ethanol were applied for inkjet printing of
transparent luminescent layers on polymer substrates. Ethanolic
dispersions of LaPO4:Ce,Tb nanoparticles were used to realize
a fully transparent dielectric barrier discharge lamp as a
prototype of a “luminescent window”.727 Cao et al.728 prepared
iron hydroxyl phosphate (NH4Fe2(PO4)2OH·2H2O) nano-
structures with a variety of morphologies such as solid
microspheres, microspheres with the core in the hollow shell,
and double-shelled hollow microspheres by the one-step
microwave-solvothermal ionic liquid method. In this method,
Fe(NO3)3·9H2O and (NH4)2HPO4 were used as the reactants
in the presence of an ionic liquid [BMIM][BF4]. The resultant
reaction system was microwave-heated at 160 °C for 1 h. The
effects of the experimental parameters on the morphology and
crystal phase of the products were investigated. The ionic liquid
[BMIM][BF4] significantly influenced the morphology and
crystal phase of the product. Starlike structures of
Fe5(PO4)4(OH)3·2H2O were obtained without [BMIM][BF4].
Rich morphologies of NH4Fe2(PO4)2OH·2H2O obtained by
this synthetic method enabled the investigation of structural-
dependent properties such as photoluminescence, which is
important for various applications, especially in light emitting
diodes. Structural-dependent photoluminescence was observed,
and photoluminescence was observed from the double-shelled
hollow microspheres of NH4Fe2(PO4)2OH·2H2O while the
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other nanostructures did not exhibit photoluminescence, and
the underlying mechanisms were discussed.
Cobalt oxalate nanorods with diameters of ∼50 nm were
prepared using Co(CH3COO)2·4H2O, H2C2O4, and NaOH as
the reactants in the presence of an ionic liquid [BMIM][BF4]
by the rapid microwave-assisted ionic liquid method at 90 °C
for 10 min. These nanorods self-assembled to form bundles of
nanorods. It was found that both [BMIM][BF4] and microwave
heating played an important role in the formation of cobalt
oxalate nanorods.729
The microwave-assisted ionic liquid method has also been
adopted for rapid synthesis of nanocomposites. Jacob et al.730
reported a microwave-assisted ionic liquid route to the
preparation of carbon-coated Cu or Ni nanoparticles using an
ionic liquid [BMIM][BF4] for 10 min. Liu et al.731 reported the
preparation of metal (such as Pt, Rh, etc.) nanoparticles
deposited on carbon nanotubes in an ionic liquid via microwave
heating. In this method, an inorganic salt (such as H2PtCl6·
4H2O, RhCl3·2H2O, etc.) as the metal source was reduced to
metal nanoparticles by glycol in 1,1,3,3-tetramethylguanidinium
trifluoroacetate or 1,1,3,3-tetramethylguanidinium lactate by
microwave heating.
Marquardt et al.733 reported the rapid microwave-assisted
preparation (6 min, 20 W) of Ru or Rh nanoparticles deposited
on chemically derived graphene surface with relatively uniform
particle sizes (Ru 2.2 ± 0.4 nm and Rh 2.8 ± 0.5 nm) by
decomposition of the corresponding metal carbonyl precursors
under argon atmosphere in a suspension of graphene in an
ionic liquid [BMIM][BF4]. The TEM micrographs of the
products (Figure 22) show that small metal nanoparticles of Ru
and Rh with sizes of 2−3 nm were uniformly dispersed on the
graphene surface. The graphene-supported metal nanoparticles
were active and could be reused at least 10 times as catalysts for
the hydrogenation of cyclohexene and benzene under organic-
solvent-free conditions.
5. MICROWAVE-ASSISTED PREPARATION OF
NANOSTRUCTURES IN OTHER SOLVENTS
In addition to the solvents of water, polyols, and ionic liquids
that have been discussed above, many other solvents have also
been investigated for the microwave-assisted preparation of
inorganic nanostructures, which have greatly widened the
applications of microwave heating in the preparation of
nanostructured materials. A variety of organic solvents have
been adopted for the microwave-assisted preparation of
inorganic nanostructures, such as alcohols,736−776 ethylene
glycol monoalkyl ethers,777 propylene carbonate,778 ethylenedi-
amine,767,779−785 PEG with low molecular weights,786−789
methacrylate,790 DMF,770,791−799 trioctylphosphine,530 non-
adecane,800 octyl ether,800 dimethyl sulfoxide,801 acetonitrile,802
tetrahydrofuran,770 formaldehyde,803 cyclohexanone,804 hexa-
decylamine,805,806 diethanolamine,807 oleylamine,808−813 1,2-
dichlorobenzene,814 toluene,815 and pyridine.816 Various
inorganic nanostructures have been prepared by the micro-
wave-assisted method in the above-mentioned solvents, and
these nanostructures include Au,736 Ag,736,737,777,790 Cu,740,741
Pd,738,739 Ru,778,814 Rh,778 Ir,778 Mo,778 W,778 Re,778 Os,778
Fe,778 Co,778 Ge,812 Cu−Ag,742 Fe−Pt,800 Fe−Pd,800 Ni−
Co, 8 1 1 C, 7 4 3 graphene, 8 1 7 Si, 7 9 2 Se, 7 7 9 Ga 2 O 3 , 7 5 3
ZnO, 744−746,751,772,787 Al-doped ZnO, 776 CuO, 747 α-
Fe2 O 3 ,748,749 Fe 3 O4 ,748,751,773 TiO 2, 752,766 Mn3 O 4 ,750,751
CoO,751 WO3,754 CeO2,763 ZrO2,764 Eu3+:Y2O3,805 α-Ni-
(OH)2,755 BaTiO3,751 NiFe2O4,761 MnFe2O4,762 PbS,768,786,803
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Bi2S3,793,795,803 HgS,768,770,786,803
CdS,767,779−781,791,794,796,801,806 ZnS,782,803 CuS,803,807 EuS,802
Cu 3 Se 2 , 797 CdSe, 804,808 CuInS 2 , 809 Cu 2 ZnSnS 4 , 810,813
CuInSe 2 , 784,785 Cu 2 SnSe 4 , 788 CuCr 2 Se 4 , 789 Cu 2−x Te, 783
HgTe,783 Ni3P,530 Eu3+-doped amorphous calcium phos-
phate,799 Pd/carbon nanotube,815 Ag/graphene, 798 Au/
CeO2,760 Pt/TiO2,765 Pd/CeO2,760 α-Fe/Fe3−x−yMnxZnyO4,756
FeyCo1−y/Fe3−xCoxO4,771 SiO2/Cd(OH)2,757 Ag/Ag2S,769
poly(ε-caprolactone)/clay,818 and CdS/poly(N-vinylcarba-
zole).816
Among these solvents, alcohols have been most frequently
used as the solvents for the microwave-assisted synthesis of
inorganic nanostructures. Alcohols have high loss tangent (tan
δ) values; for example, ethanol has a high loss tangent value of
0.941 at 20 °C and 2.45 GHz, much larger than that of water
(0.123 at room temperature). Therefore, alcohols are excellent
microwave absorbents. Gabriel et al.25 discussed in detail the
dielectric properties of alcohols for microwave heating.
Alcohols are able to form hydrogen bonds in a way similar to
that of water at a lesser extent; thus their dielectric properties
are similar to those of water. The aliphatic alcohols also have
dipole moments that are similar to those of water. As the chain
length of the alcohol increases, the relaxation time becomes
longer. The relaxation time is not greatly influenced by the
position of the OH group in the molecule, but it significantly
decreases when the hydrocarbon chain contains a double bond
or a phenyl ring adjacent to the −CH2OH fragment.25 The
standard microwave frequency for dielectric heating of 2.45
GHz corresponds to a relaxation time of 65 ps. The commonly
used alcohols have relaxation properties that enable them to
couple effectively with this fixed microwave frequency, and they
are effective solvents for microwave heating. Because alcohols
especially with low molecular weights have usually relatively
low boiling points, the open reaction systems allow only low-
temperature chemical reactions, and the solvothermal reactions
in closed systems are beneficial for relatively high-temperature
microwave-assisted synthesis.
Abargues et al.736 reported the microwave-solvothermal
preparation of Au and Ag nanoparticles by the reduction of
HAuCl4 and AgNO3 with PVA in the solvent of a short-chain
alcohol. The reaction kinetics was especially very fast because
upon microwave exposure of only 30 s the reaction was
completed. The best results were obtained using alcohols with
lower chain lengths. Pal et al.737 prepared Ag nanoparticles with
diameters of 10 ± 5 nm using AgNO3 and PVP in ethanolic
medium under microwave irradiation at 800 W for a very short
period of time (5 s). Galletti et al.739 reported the microwave-
assisted solvothermal preparation of Pd nanoparticles with an
average size of ∼3.8 nm using Pd(CH3COO)2 and PVP in the
solvent of ethanol in a single-mode microwave oven at 100 °C
for 5 min. Nakamura et al.740 prepared Cu nanoparticles with
sizes of 5−6 nm (with the surface plasmon absorption) and 2−
3 nm (without the surface plasmon absorption) using
copper(II) octanoate and copper(II) myristate, respectively,
as the copper precursors by reduction with alcohols by
microwave heating at 170 °C for 20 min. Dar et al.741 prepared
Cu nanostructures by microwave heating a solution of copper
acetylacetonate in benzyl alcohol at 800 W for 3 min. The as-
prepared Cu nanostructures were stable against oxidation in
ambient air for several months. The Cu sample was composed
of nanospheres with diameters of ∼150 nm, and each
nanosphere was made of nanocrystals with sizes of ∼7.7 nm.
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There have been many reports on the preparation of metal
nanostructures using the microwave-assisted polyol process by
reduction of metal salts with ethylene glycol, as discussed in the
previous section. Darmanin et al.777 adopted a reducing agent
as well as a solvent containing only one hydroxyl group to
prepare Ag nanostructures by microwave heating. They
demonstrated the rapid microwave-assisted production of Ag
nanoprisms/nanoplates by a careful choice of the reducing
agent containing only one hydroxyl group such as ethylene
glycol monoalkyl ethers at 140 °C for 30 min. Careful
optimization of the reducing agent, microwave heating time,
temperature, or the ratio of PVP to AgNO3 allowed complete
conversion of nanoparticles into nanoplates/prisms. They
proposed that nanoprisms formation passes through the
formation of intermediate particles (seeds) from silver spherical
particles followed by the formation of small nanoprisms and
their growth into larger nanoprisms.
Druzhinina et al.743 investigated the microwave-assisted
solvothermal preparation of carbon nanofibers and nanotubes.
The analysis of the temperature and pressure kinetics during
microwave irradiation revealed in particular a strong influence
of the applied pressure on the formation of the product.
Different metal salt (Fe, Ni, Co) solutions in ethanol were
drop-cast or spin-coated over the Si wafer and dried in the air.
The modified substrates were exposed to microwave irradiation
(5 min at 200 W) in the presence of different carbon sources
(ethanol, butanol, 2-propanol, and EG). Ni was the most
favorable catalyst to obtain small diameters of carbon
nanofibers down to 14 nm for a short microwave heating
time of 2 min.
Schneider et al.744 prepared ZnO nanoparticles by thermal
decompostion of zinc acetylacetonato and zinc oximato
complexes, respectively, in alkoxyethanols (methoxyethanol,
ethoxyethanol, or n-butoxyethanol) by microwave heating. ZnO
hierarchical hollow spheres consisting of nanoparticles were
prepared using Zn(CH3COO)2·2H2O as the zinc source and
ethanol as the solvent by the rapid one-pot microwave-assisted
solvothermal method at 200 °C for 30 min.745 Cu-doped ZnO
nanoparticles were synthesized using Cu(CH3COO)2, Zn-
(CH3COO)2, and PVP in the solvent of ethanol by microwave
refluxing for 6 min.746
Flower-like α-Fe2O3 microspheres constructed with nano-
sheets were synthesized using FeCl3·6H2O and urea in the
solvent of ethanol via the microwave-assisted solvothermal
method at 150 °C for 30 min. 749 Tetragonal Mn 3 O 4
nanoparticles with sizes of ∼30 nm were synthesized using
KMnO4 in ethanol by the microwave-assisted solvothermal
method at ∼190 °C for 5 min.750 Metal oxide nanoparticles
such as CoO, ZnO, Fe3O4, MnO, Mn3O4, and BaTiO3 were
synthesized by reacting metal alkoxides, acetates, or acetylacet-
onates in benzyl alcohol by microwave heating at 200 °C for
0.5−3 min.751 Deshmane et al.753 synthesized mesoporous
Ga2O3 nanoparticles employing triblock copolymer (F127) and
CTAB in ethanol via microwave heating at 130 °C for 15−200
min followed by calcination at 350 or 400 °C for 10 h. The
transition from semicrystalline to fully crystalline mesophases
was observed as the microwave heating time increased from 15
to 120 min. These mesophases consisted of 3−8 nm crystallites
and unimodal pores with sizes of 3−7 nm with a specific surface
area of 360 m2 g−1. Le Houx et al.754 prepared WO 3
nanoparticles with sizes of 5−30 nm by microwave-
solvothermal treatment of tungsten chloride in benzyl alcohol
up to 210 °C followed by annealing in air. The solvothermal
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treatment was carried out by resistive or microwave heating.
When the resistive heating was used, the specific surface areas
were in the range of 20−90 m2 g−1; however, 140 m2 g−1 of
specific surface area was obtained by fast microwave heating.
CeO2 nanoparticles were prepared via a microwave-assisted
solvothermal process using Ce(NO3)3, H2O2, and PVP in
isopropanol at 250 °C for 20 min, and the obtained powder was
calcined at 400 °C for 2 h.763 Flower-like TiO2 nanostructures
were prepared using commercial TiO2 and TiCl4 in benzyl
alcohol by microwave heating at 100 °C for 1 h.766 Yttria-
stabilized zirconia nanocrystals with mean sizes between 5 and
10 nm were prepared in alcoholic solutions of yttrium and
zirconium chloride and sodium ethoxide under argon gas by
microwave solvothermal treatment at ∼160 °C for 2 min.764
Bousquet-Berthelin et al.761 prepared NiFe2O4 nanoparticles
with sizes of 4−5 nm using NiCl2·6H2O, FeCl3·6H2O, and
sodium ethoxide in ethanol by the microwave-solvothermal
method at 160 °C for 5 min. Pascu et al.762 reported a fast
microwave-assisted sol−gel chemical approach to produce
magnetic nanostructured coating of MnFe2O4 on polystyrene
beads covered with a thin Al2O3 layer at 160 °C in just a few
minutes. The reaction system contained iron(III) acetylaceto-
nate [Fe(acaca)3] and Mn(CH3COO)2 (Fe/Mn molar ratio =
2:1) in anhydrous benzyl alcohol. The method can fabricate a
stoichiometric and homogeneous MnFe2O4 on the polystyrene
template over an area of half a square centimeter on a glass slide
substrate.
Alcohols have been proven to be suitable solvents for the
microwave-assisted preparation of a variety of nanocomposites.
For example, Feng et al.765 prepared Pt nanoparticles using
H2PtCl6 in the solvent of methanol by the microwave-assisted
solvothermal approach at 120 °C for 20 min and deposited Pt
nanoparticles in situ within TiO2 nanotube arrays, and the sizes
of Pt nanoparticles could be adjusted by changing the initial
concentration of metal precursor. Caillot et al.756 prepared α-
Fe/Fe3−x−yMnxZnyO4 nanocomposites by microwave-solvother-
mal treatment of alcoholic solutions of chloride precursors and
sodium ethoxide in a short period of time (e.g., 15 s). The
nanocomposites of Fe−Co alloy/cobalt ferrite (Fe3−xCoxO4)
were prepared in alcoholic solutions of ferrous chloride, cobalt
chloride, and sodium ethoxide by the microwave solvothermal
method at 160 °C.771 As compared to the conventional
synthesis, smaller grains (100 nm as compared to 1 μm) could
be produced by microwave heating in a short period of time
(e.g., 10 s) using a less basic medium. In all of the cases, the
microstructure and the amount of metal inside the composite
were very different from the product obtained via a conven-
tional heating route.771 Liu et al.757 prepared SiO2/Cd(OH)2
composite nanotubes using water-dissolvable KCdCl3 nano-
wires, NaOH, and ethyl silicate in the solvent of ethanol by the
microwave-assisted solvothermal method at 100 °C for 1 h.
KCdCl3 nanowires were prepared by adding an aqueous
solution containing CdCl2 and KI into anhydrous ethanol at
room temperature. KCdCl3 nanowires, which are water-
dissolvable and can be easily removed by washing with water,
act as both the precursor and the template for the preparation
of SiO2/Cd(OH)2 composite nanotubes in an alkaline ethanol
solution. Gonzalez-Arellano et al.758 prepared supported iron
oxide nanoparticles using FeCl2·4H2O in ethanol by microwave
heating at 200 W for 15 min (average temperature 100 °C).
The supports used were porous (silica, MCM-41, and a mild
acidic montmorillonite clay) and nonporous biomaterials
(cellulose and chitosan). Balu et al.759 reported the micro-
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wave-assisted preparation of iron oxide nanoparticles (Fe2O3,
hematite) with sizes of 3−5 nm on silica-type mesoporous
material Si-SBA-15 as a support using FeCl2·4H2O as the iron
precursor and ethanol as the solvent at 150−200 °C for 3−5
min. They found that, in contrast to the chosen reaction
temperature, the reaction time and stirring efficiency were of
critical importance in the preparation of the supported
nanoparticles. Extended reaction time (>10 min) led to a
significant proportion of larger aggregates, while inefficient
stirring also produced low-quality nanoparticles as a result of
poor dispersion and delivery of the iron precursor to the
mesoporous support. Yang et al.769 prepared porous Ag/Ag2S
hybrid nanotubes by microwave-assisted surface sulfidation of
Ag2CO3 nanorods. This process is facile and rapid, and only
involves the reaction of Ag2CO3 nanorods with thioacetamide
in ethanol under microwave irradiation at 400 W for 15 min.
The Ag content in porous Ag/Ag2S hybrid nanotubes could be
tuned by varying experimental parameters such as the
thioacetamide concentration.
In addition to alcohols, which have been commonly used as
the solvents, other solvents have also been adopted for the
microwave-assisted preparation of inorganic nanostructures.
Vollmer et al.778 reported the microwave-assisted preparation of
nanoparticles of transition metals by using propylene carbonate
as the solvent, which is an established industrial and low-priced
solvent. They have demonstrated that biodegradable propylene
carbonate can be used as a solvent and stabilizing medium for
the preparation of nanoparticles of transition metals including
Ru, Rh, Ir, Mo, W, Re, Os, Fe, and Co. Stable nanoparticles
with small and uniform particle sizes (typically <5 ± 1 nm)
were obtained by rapid (3 min) and energy-saving (50 W)
microwave heating under argon atmosphere from the metal−
carbonyl precursors in propylene carbonate. Nguyen et al.800
reported the microwave-assisted preparation of Fe−Pt and Fe−
Pd nanoparticles using Na2Fe(CO)4 and platinum acetylacet-
onate Pt(acac)2/Pd(acac)2 in nonadecane or octyl ether. By
varying the solvent and surfactant, the microwave-assisted
reactions were advantageous for the rapid production of
monodisperse face centered cubic (fcc) Fe−Pt nanoparticles,
which could be converted to the face centered tetragonal (fct)
phase at 364 °C. Microwave reactions at a high pressure in a
closed system led to the direct formation of a mixture of fcc and
fct Fe−Pt nanoparticles. The fct nanoparticles had a particle
size of ∼24 nm and a strong coercivity, indicating ferromagnetic
behavior.
Sridhar et al.817 prepared graphene sheets by combining
chemical treatment and microwave irradiation using natural
graphite, ammonium peroxy disulfate, and H2O2 in a domestic
microwave oven at 500 W for 1.5 min to produce strong
expansion of the graphite worm in the thickness direction.
Under microwave irradiation, the precursors exfoliated rapidly,
accompanied by lightening. Atkins et al.792 reported the
microwave-assisted production of amine-terminated Si nano-
particles through the reaction of Na4Si4 or Mn-doped Na4Si4
with NH4Br in the presence of the capping ligand C3H5N,
C3H7N, or C11H23N in the solvent of DMF. Uniform 3-
aminopropyl-terminated and 3-aminopropenyl-terminated Si
nanoparticles with average diameters of 2−3 nm were obtained.
Reaction temperature of 250 °C for 10 min or reactions with a
power of 200 W for 20 min were found to be the optimal
conditions for the formation of Si nanoparticles. The
microwave-assisted solvothermal method was reported for the
preparation of Se nanorods with diameters in the range of 30−
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150 nm using sodium selenite and NaBH4 in ethylenediamine
at 100 °C for 1 h.779
Ethylenediamine has been adopted as the solvent to prepare
metal chalcogenide nanostructures by microwave heating. For
example, CdS nanorods were prepared using CdCl2, thiourea,
and glutathione in ethylenediamine by the microwave-assisted
solvothermal method at 160 °C for 3 h.779 CdS nanowires with
diameters of ∼4 nm were prepared using a complex of
cadmium-1-pyrrolidine dithiocarboxylic acid ammonium in
ethylenediamine under microwave irradiation in ambient air
for 1 min.780 CdS nanoribbons were prepared using CdCl2·
2.5H2O and 1-pyrrolidine dithio carboxylic acid ammonium salt
in ethylenediamine under microwave irradiation for 10 min in
ambient air.781 Radial ZnS nanoribbons with widths of 10−20
nm and a typical thickness of 3 nm were synthesized in
ethylenediamine via the microwave-solvothermal method,
combined with the thermal treatment in nitrogen gas flow.782
Palchik et al.783 synthesized nanoparticles of Cu2−xTe and
HgTe adopting elemental Te, CH3COOCu, and mercury
acetate in the solvent of ethylenediamine by microwave
refluxing for 1−2 h. In the case of the preparation of
Cu2−xTe, the product was a complex of Cu, Te, and
ethylenediamine, which decomposed into Cu2−xTe by anneal-
ing at 280 °C under Ar for 2 h. CuInSe2 nanostructures with a
rodlike or platelike morphology were prepared in ethylenedi-
amine by the microwave-assisted solvothermal method at 180
°C for 5−30 min.784
DMF has also been adopted as the solvent for the
microwave-assisted synthesis of nanostructured metal chalco-
genides. Majumder et al.794 reported the microwave-assisted
synthesis of CdS nanocrystals through the reaction of
Cd(CH3COO)2 with thiourea in the presence of capping
agents (1-butanethiol and 2-mercaptoethanol) in DMF; the
number of microwave heating was varied to control the size and
size distribution of the thiol-capped CdS nanocrystals. Karan et
al.796 reported the microwave-assisted synthesis of CdS
quantum dots with sizes of 2.9−5.5 nm using Cd-
(CH3COO)2·2H2O, thiourea, and poly(methyl methacrylate)
in DMF at 900 W for 20−30 s. He et al.793 prepared Bi2S3
nanowhiskers through the reaction between Bi(NO3)3·5H2O
and thiourea in the presence of PVP in the solvent of DMF via
a microwave-assisted route. Bi2S3 nanorods were prepared using
bismuth citrate, thiourea, and CTAB in the solvent of DMF by
microwave heating at 200 °C for 5 min.795 β-HgS nanoparticles
with sizes of 8−23 nm were prepared using Hg(CH3COO)2·
2H2O and thiourea in different solvents by microwave refluxing,
and the solvents used were absolute ethanol, tetrahydrofuran,
distilled water, DMF, and 20% DMF aqueous solution,
respectively.770 Cu3Se2 nanoplates with a thickness of 17 nm
were synthesized through a microwave-enhanced reaction
between Se and copper(I) oleate in DMF at 100 °C for 1 h.797
Other solvents have also been used in the microwave-assisted
synthesis of nanostructured metal chalcogenides. Ferrer et al.801
reported turning “on” and “off” nucleation and growth of CdS
clusters and nanoparticles with diameters ranging from 1.6 to
over 250 nm from the microwave-assisted reaction of
Cd(CH3COO)2 with dimethyl sulfoxide. Dimethyl sulfoxide
acted as the solvent and a source of sulfide ions. The formation
of CdS was controlled by turning on and off microwave energy
supply. The extent of the nucleation and growth was controlled
by the supply of sulfide ions from the reaction of Cd2+ ions and
dimethyl sulfoxide during exposure to microwave radiation.
Marx Nirmal et al.806 used the complex of cadmium with
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pyrrolidine dithiocarbamate Cd(pdtc)2 as a single source
precursor for the synthesis of CdS nanoparticles by micro-
wave-assisted thermal decomposition of the complex in the
solvent of hexadecylamine. The microwave irradiation failed to
decompose the complex Cd(pdtc)2 without the addition of a
polar solvent even after heating for 5 min. However, the
addition of a small amount of DMF to the reaction system and
microwave heating for 1 min with a power of 800 W resulted in
the formation of CdS nanoparticles. CdS nanoparticles with a
disordered close-packed structure and an average size of 5 nm
were obtained under microwave irradiation; in contrast,
wurtzite hexagonal CdS nanorods with an average size of ∼3
nm in width and 15 nm in length were obtained by the
conventional heating at 150 °C for 30 min. In the case of the
conventional heating, the decomposition rate was very slow,
and the nanoparticles grew in a direction leading to nanorods.
Low molecular weight PEG-200 was also used as a solvent
for the preparation of PbS and HgS nanoparticles with average
sizes from 20 to 30 nm using the reactants of Pb(CH3COO)2·
3H2O, Hg(CH3COO)2, and S powder by microwave heating
for 20 min.786 Liu et al.807 reported a microwave-assisted Cu-
complex transformation route for the preparation of CuS
nanotubes. Using Cu-complex Cu(TU)Cl·0.5H2O (TU =
thiourea) nanowires as the self-sacrificial template formed
under ambient conditions, CuS nanotubes with a rectangular
cross-section were synthesized in diethanolamine. The diameter
of CuS nanotubes with a rectangular cross-section could be
tuned through changing experimental parameters. Furthermore,
cone-like CuS nanotubes were also prepared by adopting Cu-
EBT (EBT = eriochrome black T) complex nanorods as
precursors. CuS nanotubes with rectangular cross sections were
found to be effective as nonenzymatic glucose sensors. Liao et
al.803 reported the microwave-assisted synthesis of nanocrystal-
line metal sulfides including CuS, HgS, ZnS, Bi2S3, and PbS
with different shapes and different particle sizes using
corresponding metal salts and thioacetamide in the solvent of
formaldehyde. Hasegawa et al.802 prepared EuS nanoparticles
with an average size of 8 nm by microwave refluxing
decomposition of a single source precursor (PPh4)[Eu-
(S2CNEt2)4]·2H2O in acetonitrile for 6 h. Firth et al.804
reported the microwave-assisted synthesis of CdSe nanocrystals
using Cd(CH3COO)2·H2O and Se in cyclohexanone, and the
reaction mixture was heated to 145 °C for varying lengths of
time (between 30 s and 15 min). The particle size was
regulated by adjusting the reaction time. When the reaction
time was restricted to less than 1 min, it was possible to isolate
CdSe nanocrystals with an average diameter of 2 nm, while 6
nm CdSe nanocrystals were produced for longer than 10 min.
Wang et al.808 prepared red-emitting CdSe quantum dots with
sizes ranging from 6.0 to 13.4 nm adopting B2Se3 and CdCl2 as
the reactants in oleylamine by microwave heating; the particle
size was controlled mainly by changing reaction temperatures
from 190 to 270 °C. The smallest quantum dots exhibited the
zinc blende structure, while larger particles showed the wurtzite
structure.
Nanostructured ternary and multinary metal chalcogenides
have also been prepared in various solvents by the microwave-
assisted method. Pein et al.809 prepared CuInS2 nanoparticles
using CuI, InCl3, and elemental S in the solvent of oleylamine,
and a microwave heating time of only 1.5 min resulted in the
rapid formation of CuInS2 nanoparticles with sizes of 3−4 nm.
Yang et al.810 prepared Cu2ZnSnS4 nanoparticles with sizes of
∼10−15 nm using Cu(NO3)2·3H2O, Zn(NO3)2·6H2O, SnCl4·
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5H2O, and S powder in oleylamine by microwave heating at
260 °C for 30 min followed by annealing at 350 °C under
nitrogen gas flow. Lee et al.785 prepared CuInSe2 nanostruc-
tures with different morphologies using CuCl2, InCl3·4H2O,
and Se powder in ethylenediamine by a microwave-assisted
solvothermal process at 180 °C for 1 h. The optimum
crystallinity was obtained at 180 °C with 0.02 M Cu2+ ions.
When Cu(CH3COO)2 was used as the copper source, CuInSe2
particle size was dramatically reduced. Moreover, the synthesis
at 1 L scale of the reactants gave the particle size of 20 nm,
which was smaller than that of small scale synthesis (23−35
nm). Grisaru et al.788 prepared Cu2SnSe4 nanoparticles using
CuCl (or CuCl2·2H2O), Sn, and Se in PEG as the solvent by
microwave heating at 900 W for 2 h, and the precursor was
annealed under argon at 450 °C for 12 h. It was found that the
reactants did not react in EG, tri-, or tetraethylene glycol. Kim
et al.789 prepared CuCr2Se4 nanoparticles from the chemical
reactions of CuCl, Cr(CH3COO)3, and Se in PEG-400 under
microwave irradiation at 540 W for 1 h in argon atmosphere.
Different kinds of nanocomposites have been prepared by
the microwave-assisted method in various solvents. Yamauchi et
al.811 reported the microwave-assisted synthesis of face-
centered cubic Ni/Co (core/shell) nanoparticles using Ni-
(CH3COO)2 and cobalt(II) formate complexes in oleylamine.
The as-prepared product was composed of a Co-rich shell and a
Ni-rich core. The shape of Ni/Co nanoparticles could be varied
using different nickel precursors (acetate or formate com-
plexes), and the shape of the Ni core played a key role in
determining the final shape of Ni/Co nanostructures. Liu et
al.798 prepared the Ag nanoparticles/graphene nanocomposite
by one-pot microwave-assisted reduction using a DMF solution
of graphene oxide and AgNO3. Cano et al.815 reported a fast
one-step microwave refluxing synthesis of the nanocomposite
of Pd nanoparticles/multiwalled carbon nanotubes by decom-
position of the complex Pd2(dba)3CHCl3 (dba = trans,trans-
dibenzylideneacetone) in the presence of carbon nanotubes in
the solvent of toluene under argon atmosphere. High loadings
of Pd nanoparticles (up to 40 wt %) having sizes between 3 and
5 nm were deposited on the surface of carbon nanotubes within
2 min. The reaction time was significantly shortened by
microwave heating (only 2 min), which required 2 h under the
conventional heating at the same temperature (115 °C). Wada
et al.790 prepared Ag nanoparticles using C13H27COOAg in
reactive methacrylate monomer under microwave irradiation.
Successive polymerization of the monomer containing the
resulting Ag nanoparticles produced the nanocomposite
comprising Ag nanoparticles dispersed in the polymer matrix.
He et al.816 prepared CdS/poly(N-vinylcarbazole) nano-
composites by microwave heating at 300 W for 5 min in
which the polymerization of N-vinylcarbazole and the
formation of CdS nanoparticles with sizes of ∼10−20 nm
occurred simultaneously, using N-vinylcarbazole, azobisisobu-
tryonitrile, Cd(CH3COO)2·2H2O, and thiourea as the reactants
and pyridine as the solvent. Chen et al.799 prepared amorphous
calcium phosphate (ACP)/polylactide-block-monomethoxy-
(poly(ethylene glycol)) (PLA−mPEG) hybrid nanoparticles
using CaCl2, Na2HPO4·12H2O, and PLA-mPEG in aqueous
solution (pH value was adjusted to 10 using ammonia).
Subsequently, the microwave-assisted solvothermal approach
was adopted for the preparation of ACP porous nanospheres by
using ACP/PLA−mPEG hybrid nanoparticles in DMF at 200
°C for 1 h, europium-doping was performed to enable
photoluminescence function of ACP porous nanospheres, and
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a high specific surface area of the europium-doped ACP
(Eu3+:ACP) porous nanospheres was achieved (126.7 m2 g−1).
In vitro drug release experiments indicated that the ibuprofen-
loaded Eu3+:ACP porous nanospheres had a slow and sustained
drug release property in simulated body fluid. It was found that
the cumulative amount of released drug had a linear
relationship with the natural logarithm of release time (ln(t)).
The as-prepared Eu3+:ACP porous nanospheres were bioactive,
and could transform to hydroxyapatite during drug release in
simulated body fluid.
6. MICROWAVE-ASSISTED PREPARATION OF
NANOSTRUCTURES IN MIXED SOLVENTS
The properties of the solvents have significant effects on the
formation of inorganic nanostructures under microwave heating
conditions. Different solvents interact very differently with
microwaves because of variations in solvent polarities,
dielectricity, and other properties. The appropriate selection
and use of mixed solvents will greatly expand the application
range of the microwave-assisted rapid preparation of inorganic
nanostructures. The different combination and the volume ratio
of the selected mixed solvents will also provide additional
experimental parameters for control over the chemical
composition, structure, size, morphology, and self-assembly of
microwave-synthesized inorganic nanostructures.
6.1. Binary Solvent Systems
6.1.1. Water/Polyols. Polyols have several −OH functional
groups attached to the carbon backbone, they are excellent
solvents for microwave heating with high loss tangent (tan δ)
values, and their abilities to absorb microwaves are generally
much better than that of water. The combination of water and
polyols will certainly enhance the absorption of microwaves as
compared to that in the case of using water as the only solvent.
On the other hand, polyols are highly miscible with water, and
polyol molecules are able to form intermolecular hydrogen
bonds with each other and with neighboring water molecules in
solution. The polyol compounds usually have high viscosities
due to strong hydrogen bonding.25 However, some reactants
have limited solubilities in polyols as the solvents especially
with high molecular weights. The addition of water in polyols
will greatly increase the solubilities of many reactants.
Because of their advantages, the mixed solvents of polyols
and water have been frequently used for the microwave-assisted
preparation of inorganic nanostructures, including Pt,819 Cu,820
Ni,821,822 Co,823 carbon,824,825 Pt−Ru,819 Pt/C,826−832 Pt/
diamond,833 Pt/carbon nanotube,832,834−836 Pt/carbon nano-
tube/carbon paper, 837 Pt/graphene, 838−840 Pt−Ru/gra-
phene,841 Pd/C,828 Ag/carbon paper,842 ruthenium oxide/
carbon nanotube,843 α-Fe2O3,844,845 Fe3O4,846 ZnO,847−849
copper oxide, 850−852 TiO2 ,853 CeO 2,854,855 In2O 3:Sn,856
SnO2:F,857 WO3·(H2O)0.33,858 cobalt(II) acetate hydroxide,369
Cd(OH)2,859 Bi2S3,860 RuxSey,861 Ru85Se15,862 Bi2Te3,863,864
Sb2Te3,865,866 CaCO3,867,868 CaHPO4,869 BiPO4,380 RE:YPO4
(RE = Eu, Ce, Tb, and Ce + Tb),870 Tb:CePO4,871 GdPO4,872
Eu:GdPO4,872 LiFePO4,873 LiFe1−x(VO)xPO4,874 BaTiO3,875
Nd-doped SrTiO 3 , 8 7 6 (Ba,Sr)TiO 3 , 8 7 7 CaMoO 4 , 8 7 8
FeMoO4,879 Zn1−xCoxAl2O4,880 CoFe2O4,881,882 MnFe2O4,882
Bi2GeO5,883 ZrO2-doped Al2O3,448 Cox(OH)y(X)z·nH2O (X =
anion),884 NaYF4:Yb,Er,885 Ce- and Tb-doped BaYF5,886 SnO2/
graphene,841 IrxSey/C,887 Ru85Se15/carbon nanotube,888 Pt3Te/
C,889 Pt/CeO2/C,890 Fe3O4/HAP,891 Fe3O4/zeolite,892 ZnO/
zeolite,892 and SnS2/SnO2.893
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Various metal nanostructures have been successfully
prepared by the microwave-assisted method in mixed solvents
of EG and water. Liu et al.819 prepared Pt (4.7 nm) and Pt−Ru
(4.5 nm) nanoparticles using H2PtCl6 and/or RuCl3 in mixed
solvents of EG and water by a microwave-assisted process at
170 °C for 1 min. Xu et al.820 prepared dimethylglycoxime
functionalized Cu nanoparticles using Cu(CH3COO)2·H2O
and dimethylglycoxime in mixed solvents of EG and water by
microwave refluxing heating under ambient air at a power of
365 W for 30 min, and the as-prepared Cu nanoparticles were
used to construct a glucose sensor. The microwave-assisted
preparation of Ni nanowires with a necklace-like morphology
was reported by Tang et al.821 NiCl2·6H2O, hydrazine
monohydrate, and PVP were used as starting reagents, and
EG and water were used as the mixed solvent. The as-prepared
Ni nanowires consisted of many nanoparticles with an average
size of ∼25 nm. Ni nanostructures with various morphologies
including spheres, chains, and irregular particles with porous
surfaces were also obtained by adjusting experimental
parameters. Tang et al.822 prepared polycrystalline Ni nano-
wires using NiCl2·6H2O, PVP, hydrazine (85 wt %), and EG by
microwave heating at a power of 400 W for 2 min and another
4 min at 150 W. The diameters of Ni nanowires were
controllable in a wide range of 70−380 nm via the
concentration of precursor solutions, and the diameters of the
nanowires as well as those of the contained particles increased
linearly with the concentration. The nanowires had rough
surfaces at low concentrations but became smoother at high
concentrations. Shojaee et al.823 prepared flower-like Co
nanostructures constructed by nanosheets in mixed solvents
of water and EG under microwave irradiation at 900 W for less
than 10 min.
There have been many papers in the literature reporting on
the microwave-assisted synthesis of nanocomposites consisting
of Pt nanoparticles and carbon-based support in mixed solvents
of water and polyols. Chen et al.826 prepared Pt nanoparticles
(3.5−4.0 nm) supported on commercial carbon using H2PtCl6·
6H2O and KOH in mixed solvents of EG and water by a
microwave-assisted process at 700 W for 1 min. Wang et al.827
adopted a similar microwave-assisted method for the
preparation of the Pt/C nanocomposite. It was found that
the particle size and size distribution of Pt nanoparticles were
greatly influenced by the microwave irradiation duration
(heating temperature). Temperature in the reacting beaker
was 132 ± 2, 163 ± 2, 175 ± 2, and 186 ± 2 °C for microwave
heating times of 0.5, 1, 1.5, and 2 min, respectively. Liu et al.828
prepared Pt or Pd nanoparticles supported on commercial
carbon using H2PtCl6·6H2O or PdCl2 in mixed solvents of EG
and water by a microwave-assisted process for 50 s, and the
average particle size of Pt and Pd nanoparticles was 4 and 5 nm,
respectively. Zhou et al.829 fabricated Pt nanoparticles
supported on the mesoporous carbon using H2PtCl6, NaOH,
and CTAB in mixed solvents of EG and water by a microwave-
assisted process at 700 W for 1 min, wherein CTAB was
expected to improve the wettability of carbon support as well as
the dispersion of Pt nanoparticles. It was found that Pt
nanoparticles were uniform in size and highly dispersed on the
mesoporous carbon support. Zhao et al.831 reported that
CH3COONa had an effect on the size of Pt nanoparticles
prepared in mixed solvents of EG and water under microwave
irradiation. Acetate-stabilized Pt nanoparticles supported on
commercial carbon were obtained using H2PtCl6·6H2O and
CH3COONa by microwave heating at 800 W for 1 min, and
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Figure 23. SEM micrograph of as-prepared indium tin oxide (In2O3:Sn) nanocrystals and size distribution. Reprinted with permission from ref 856.
Copyright 2008 Elsevier B.V.
the mean size of Pt nanoparticles was 5.1, 4.3, 3.5, and 2.8 nm,
respectively, when 0, 0.1, 0.3, and 0.5 mL of 1.0 M
CH3COONa solution was used. Li et al.834 prepared Pt
nanoparticles with different sizes supported on carbon
nanotubes using K2PtCl6 and KOH in the presence of carbon
nanotubes in mixed solvents of EG and water with different pH
values by a microwave-assisted process at 800 W for 1 min. It
was found that the pH value had an effect on the particle size,
and that Pt nanoparticles became smaller and more uniform
when the pH value increased from 3.4 to 9.2. Sharma et al.838
prepared the nanocomposite consisting of Pt nanoparticles with
sizes of several nanometers and graphene using graphene oxide,
K2PtCl6, and KOH in mixed solvents of EG and water by a
microwave-assisted process at 700 W for 50−100 s. Guo et
al.839 prepared the Pt nanoparticle/graphene nanocomposite
using graphene oxide, Pt precursor, and poly(methacrylic acid
sodium salt) in mixed solvents of EG and water by a
microwave-assisted process at 800 W for 1.5 min. Liao et
al.840 prepared the Pt/graphene nanocomposite in mixed
solvents of 1,2-propanediol and a small amount of water by
one-pot microwave-assisted process at 170 °C for 5−20 min.
For short reaction times, the as-prepared Pt nanoparticles were
small, well separated, and uniformly deposited on graphene.
Prolonged microwave irradiation led to dense dispersion of Pt
nanoparticles and the formation of some aggregated nano-
particles, and eventually to continuous connecting agglomer-
ates.
Nanostructures of metal oxides have also been prepared by
the microwave-assisted method in mixed solvents of water and
polyols. Deshmukh et al.844 prepared bundles of α-Fe2O3
nanorods using Fe(NO3)3·9H2O in mixed solvents of water
and pentaerythritol by a microwave-assisted solvothermal route
at 130 °C for 15 min. Wang et al.846 prepared Fe3O4
nanosheets using FeSO4·7H2O and NaOH in mixed solvents
of EG and water by microwave refluxing heating, and the iron
salt, ratio of OH− to iron ions, and heating method had effects
on the morphology or crystalline phase of the product.
For the microwave-assisted synthesis of ZnO nanostructures,
Zhu et al.847 prepared ZnO hierarchical nanostructures with
straw-bundle-like, chrysanthemum-like, and oat-arista-like
morphologies and nanorod-based microspheres using Zn-
(CH3COO)2·H2O in mixed solvents of EG and water via
microwave heating. Zhang et al.848 reported the microwave-
assisted solvothermal synthesis of ZnO structures with a variety
of morphologies using Zn(CH3COO)2·2H2O in a mixture of
water and EG in a short period of time. By changing the volume
ratio of water to EG, the morphology of ZnO could be
6516
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controlled, and different morphologies of ZnO, such as rods,
hexagonal prisms, peanuts, butterflies, and hierarchical nano-
spheres, could be obtained. Edrissi et al.849 prepared deer horn-
like ZnO nanostructures via microwave heating bis(2-
pyridinethiol N-oxide) zinc(II) complex in a mixture of EG
and water.
Well-crystallized birnessite nanosheets containing K+ in the
interlayers were prepared using KMnO4 and KOH in mixed
solvents of EG and water by microwave heating at 90 °C for 10
min, and ethylene glycol was used as both a solvent and a
reducing agent.894 Mn3O4 nanoparticles with sizes less than 50
nm were prepared using MnCl2·4H2O and NaOH in mixed
solvents of distilled water and EG by microwave refluxing with
a power of 20 W for the total pulsed microwave irradiation time
of 5 min.895 Shirke et al.854 synthesized cerium oxide
nanoparticles with an average particle size of 9 nm using
cerium nitrate, propylene glycol, and ammonia by microwave
heating. Zawadzki et al.855 prepared CeO2 nanoparticles with an
average particle size of ∼3 nm using Ce(NO3)3·6H2O and
hexamine (C6H12N4) in mixed solvents of diethylene glycol and
water by the microwave-solvothermal method under the
pressure of 10 bar for 1 h.
Hammarberg et al.856 prepared indium tin oxide (ITO)
nanoparticles using InCl3 ·4H 2 O, SnCl 4 ·5H 2 O, and N-
(CH3)4OH·5H2O in mixed solvents of diethylene glycol and
water by microwave heating at 200 °C for 2 h under ambient
pressure. The SEM micrograph of as-prepared ITO nanocryst-
als and size distribution are shown in Figure 23. The as-
prepared suspension of ITO in diethylene glycol was colloidally
stable within weeks and exhibited a transparent appearance
with a bright blue color (Figure 23). The average particle
diameter of ITO nanocrystals was 15 nm with a narrow size
distribution (Figure 23). The BET specific surface area of
powdered ITO nanocrystals was measured to be 56.1 m2 g−1.
Avadhut et al.857 prepared fluorine-doped tin oxide (SnO2:F)
nanoparticles with different doping levels in mixed solvents of
diethylene glycol and water by the microwave-assisted approach
at 200 °C for 1 h, and SnCl4·5H2O, N(CH3)4F·4H2O, and
N(CH3)4OH·5H2O were adopted as the reactants.
Nanostructures of ternary and multinary metal oxides have
also been successfully prepared in mixed solvents of water and
polyols by the microwave-assisted method. Lee et al.875
prepared BaTiO3 nanoparticles using Ba(OH)2·8H2O and
amorphous titanium hydrous gel as precursors in mixed
solvents of 1,4-butanediol and water by a microwave-assisted
solvothermal process for a short period of time. Typically, the
microwave-assisted reaction was accomplished within 2 h at
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220 °C against 12 h required in the conventional heating
approach. They detected the metastable cubic phase by XRD
while locally symmetric tetragonal phase by Raman spectros-
copy in the case of the conventional processing. In contrast,
they detected the coexistence of tetragonal and cubic phases by
XRD and only tetragonal phase by Raman spectroscopy in the
case of the microwave-assisted processing. The TEM analysis
indicated typical particle size distribution in the range of ∼20−
80 nm for conventionally processed powder while that in the
range of ∼20−50 nm for the microwave processed powder.
Zheng et al.876 synthesized mesoporous Nd-doped SrTiO3
nanospheres and nanoplates with high specific surface areas
using tetra-n-butyltitanate, Sr(NO3)2, Nd(NO3)3, and NaOH in
mixed solvents of EG and deionized water by the microwave-
assisted solvothermal method at 200 °C for 10 min.
Mesoporous Nd-doped SrTiO3 nanospheres were obtained at
lower concentrations of the reactants. However, the product
consisted of nanoplates when the concentrations of the
reactants were increased. Yang et al.877 synthesized (Ba,Sr)TiO3
nanocrystals with average particle sizes ranging from 20 to 80
nm using TiOCl2, Ba(OH)2, Sr(NO3)2, and ammonia in mixed
solvents of 1,4-butanediol and water through a microwave-
assisted approach at 800 W within a short reaction time (∼1
min).
Marques et al.878 synthesized nanostructure-assembled
CaMoO4 materials using Ca(CH3COO)2·H2O and H2MoO4
in mixed solvents of deionized water and EG with different
ratios by the microwave-assisted solvothermal method at 140
°C for 1 h. Corn-cob-like CaMoO4 structures were obtained in
only aqueous solution, and these structures essentially consisted
of small aggregated particles with an octahedral shape. In the
synthesis containing 25 mL of EG and 75 mL of water, two
distinct types of microcrystals (corn cob and dumbbell shapes)
were observed. Zhang et al.879 synthesized FeMoO4 hierarchical
hollow microspheres by the reaction between Fe(NO3)3·9H2O
and (NH4)6Mo7O4·4H2O in mixed solvents of water and
glycerol via microwave heating at 190 °C for 10 min. The as-
prepared hierarchical microsphere had a hollow interior, and
the shell was composed of many irregular nanoparticles. It was
proposed that the self-assembly of FeMoO4 nanoparticles at the
water/gas interface was responsible for the formation of
hierarchical hollow microspheres.
Zn1−xCoxAl2O4 (x = 0, 0.5, 1.0) nanoparticles were
synthesized using Zn(CH3COO)2·2H2O, Co(CH3COO)2·
2H2O, and Al[OCH(CH3)2]3 in mixed solvents of 1,4-
butanediol and water under microwave-assisted solvothermal
conditions at 200 °C for 1 h, and the obtained precursors were
calcined at 550 and 1100 °C for 3 h.880 CoFe2O4 nanoparticles
with an average size of ∼5 nm were obtained by coprecipitation
using Co(CH3COO)2·4H2O, FeCl3, and CH3COONa·3H2O in
mixed solvents of 1,2-propanediol and deionized water by
microwave heating at 160 °C for 1 h.881 MFe2O4 (M = Mn,
Co) nanoparticles with diameters less than 10 nm were
prepared using ferric salts in mixed solvents of EG and water by
microwave refluxing for 10 min.882 A microwave-assisted
refluxing route has been used to synthesize 5 nm thickness
nanoflake-assembled flower-like microspheres of cobalt hydro-
talcite such as the compound Cox(OH)y(X)z·nH2O (X =
anion) using Co(NO3)2·6H2O and urea in mixed solvents of
EG and deionized water at 85 °C for various periods of times
(15, 30, and 90 min).884
Spheroidal vaterite CaCO3 structures composed of irregular
nanoparticles with an average size of ∼70 nm were synthesized
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Review
by a microwave-assisted reaction between Ca(CH3COO)2 and
(NH4)2CO3 in mixed solvents of EG and water at 90 °C for 10
min.867 Vaterite CaCO3 structures with various morphologies
were rapidly synthesized via the reaction between Ca-
(CH3COO)2 and Na2CO3 in the presence of CTAB or SDS
in the water/EG system by the microwave-assisted method at
100 °C for 8−30 min.868 It was found that the microwave
heating, reaction time, surfactant, and solvent played important
roles in the morphology of vaterite. Various vaterite structures
with dagger-like, bicone-like, shuttle-like morphologies and
microspheres self-assembled from nanoparticles were obtained
by adjusting the experimental parameters. The experiments
indicate that when the reaction time is prolonged, vaterite, as a
less stable polymorph that is stabilized kinetically, will
transform into calcite.868
Ma et al.869 reported the microwave-assisted synthesis of
CaHPO4 with flower-like and bundle-like morphologies using
CaCl2·2.5H2O and NaH2PO4 in the presence of SDS in mixed
solvents of EG and water at 95 °C for 1 h. It was found that the
molar ratio of water to EG and reaction time had significant
effects on the size and morphology of the product. BiPO4
nanoparticles and nanorods were synthesized using Bi(NO3)3·
5H2O and NaH2PO4·2H2O in mixed solvents of glycerol and
water by microwave heating for 15 min (80% of 800 W).
However, the rice-like morphology of BiPO4 was obtained in
mixed solvents of EG/water or diethylene glycol/water.380
Rodriguez-Liviano et al.870 prepared mesoporous tetragonal
RE:YPO4 nanostructures (RE = Eu, Ce, Tb, and Ce + Tb) with
a lenticular morphology by a microwave-assisted homogeneous
precipitation process at temperatures ranging from 80 to 120
°C from EG solutions containing yttrium acetylacetonate and
H3PO4 (85%). Rodriguez-Liviano et al.872 reported the
microwave-assisted solvothermal synthesis of GdPO4 and
Eu:GdPO4 nanocubes using gadolinium (europium) acetyla-
cetonate and H3PO4 in mixed solvents of butylene glycol and
water at 120 °C (heating rate 14 °C min−1) for 1 h. Figure 24
Figure 24. TEM micrographs of GdPO4 and Eu:GdPO4 nanocubes
prepared by microwave heating at 120 °C for 1 h using buthylene
glycol solutions containing Eu(acac)3, Gd(acac)3 (Gd + Eu = 0.02 mol
L−1), and H3PO4 (0.15 mol L−1) with different Eu content: 0%
(GdPO4) and 5% (Eu0.05Gd0.95PO4). Reprinted with permission from
ref 872. Copyright 2012 American Chemical Society.
shows TEM micrographs of GdPO4 and Eu:GdPO4 nanocubes
obtained using butylene glycol solutions containing Eu(acac)3,
Gd(acac)3 and H3PO4 by microwave heating at 120 °C for 1 h.
The as-prepared GdPO4 and Eu:GdPO4 nanocubes were
uniform in size with edge sizes of ∼75 ± 10 nm, and were
highly crystalline with a tetragonal structure. In comparison,
when keeping the same concentrations of reagents and reaction
conditions but using the conventional heating, long nanowires
with a hexagonal structure were obtained, although a small
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number of nanocubes were also formed. The nature of the
polyol solvent was another key factor for the formation of
nanocubes. When butylene glycol was replaced by EG, the
product was composed of bigger spheroidal particles with
relatively uniform sizes, and a mixture of crystalline phases
(tetragonal and monoclinic) was obtained. Murugan et al.873
synthesized olivine LiFePO4 nanorods using LiOH, Fe-
(CH3COO)2, and H3PO4 in tetraethylene glycol by a rapid
microwave-solvothermal approach at 300 °C for 5 min.
Harrison et al.874 synthesized LiFe1−x(VO)xPO4 (x = 0−0.25)
nanostructures using stoichiometric ratios of LiOH, Fe-
(CH3COO)2, H3PO4, and VO(OC3H7)3 in tetraethylene glycol
by the microwave-solvothermal process at the temperatures
between 260 and 280 °C (power 600 W) within 10 min. The
morphologies of LiFe1−x(VO)xPO4 had several types including
rods, plate-like particles, and spheres. LiFe1−x(VO)xPO4 is
thermally unstable and a metastable phase that is difficult to be
synthesized by the conventional method.
Nanostructured chalcogenides have also been prepared by
the microwave-assisted method in mixed solvents of water and
polyols. Jiang et al.860 prepared Bi2S3 nanostructures with
urchin-like and rod-like morphologies using Bi2O3, HCl, and
Na2S2O3·5H2O in mixed solvents of EG and water by
microwave heating at 190 °C for 30 s. Urchin-like Bi2S3
nanostructures were obtained using SDS or in the absence of
any surfactant; however, Bi2S3 nanorods were obtained in the
presence of CTAB. Liu et al.862 prepared Ru85Se15 nano-
particles with an average size of ∼1.8 nm using RuCl3 and
Na2SeO3 in mixed solvents of EG and a small amount of water
via a rapid microwave-assisted process at 700 W for 1.5 min.
Nekooi et al.861 synthesized RuxSey nanoparticles using RuCl3·
0.5H2O, Na2SeO3·5H2O, and KOH in mixed solvents of EG
and water by microwave refluxing heating at 1000 W for 75 s
under stirring.
Bi2Te3 hollow nanospheres with diameters of 50−100 nm
were prepared using TeO2, Bi(NO3)3 and HNO3 in mixed
solvents of water and EG by microwave heating at 150 °C for
30 min.863 Bi2Te3 nanosheets and nanotubes were prepared
using Bi(NO3)3·5H2O and TeO2 in mixed solvents of EG and
water via the microwave-assisted method at 170−195 °C for
30−60 min. It was found that both the nanosheets and the
nanotubes were well-crystallized single crystals, and morphol-
ogies of the products were greatly affected by the microwave
heating temperature. A possible formation mechanism related
to the layer structure rolling was also proposed.864 Dong et
al.865 synthesized Sb2Te3 single-crystalline nanosheets with
thicknesses of 50−70 nm using SbCl3, Na2TeO3, hydrazine
hydrate, and EG by the microwave-assisted method at 200 °C
for 15 min, and the reaction mechanism was proposed. The
bulk sample of Sb2Te3 nanosheets was prepared by the spark
plasma sintering, which still consisted of Sb2Te3 nanosheets
after the spark plasma sintering and thermoelectric property
measurements, and a relatively high ZT value of 0.58 at 420 K
was obtained. They also reported the rapid microwave-assisted
solvothermal synthesis of Sb2Te3 nanostructures with a variety
of morphologies including single-crystalline nanorods, individ-
ual nanosheets, nanorods with branched ultrathin nanosheets,
and half-nanotubes constructed by self-assembly of nanocryst-
als.866 In this method, SbCl3, TeO2, hydrazine hydrate, PEG,
and EG were used as starting reagents, and the reaction system
was heated by microwaves at 200 °C for 15 min. The
morphology of Sb2Te3 nanostructures could be controlled by
simply altering the amount of hydrazine hydrate and PEG. The
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tablet samples of Sb2Te3 nanostructured powders with different
morphologies were prepared by a room-temperature pressur-
ized method, and they exhibited high Seebeck coefficients,
which were much higher than those of Sb2Te3 bulk crystals.
Mi et al.885 reported the microwave-assisted solvothermal
synthesis of NaYF4:Yb,Er nanoparticles adopting mixed
solvents of EG and water at 160 °C for 1 h. Rare earth
acetates were used as rare earth precursors, and NH4F (or
NH4HF2, NaF, ionic liquid [BMIM][BF4]) and NaCl were
used as the sources of fluorine and sodium, respectively. The as-
prepared nanoparticles were nearly ellipsoidal or spherical, with
an average size of ∼41 nm and with mixed hexagonal and cubic
structures. Lei et al.886 prepared Ce3+- and Tb3+-doped BaYF5
nanocrystals using Ba(CH3COO)2, Y(NO3)3, NH4F, Ce-
(NO3)3, and Tb(NO3)3 in mixed solvents of EG and water
by microwave heating for 10 min.
In addition to the single-phase nanostructured materials,
various nanocomposites have been successfully prepared by the
microwave-assisted method in mixed solvents of water and
polyols. Wang et al.841 prepared Pt−Ru/graphene and SnO2/
graphene nanocomposites in a mixture of EG and water by a
microwave-assisted process at 700 W for a total time of 4 min.
One of the advantages of this method is that the reduction of
graphene oxide to graphene and the formation of Pt−Ru
nanoparticles from metal precursors and SnO2 nanoparticles
from SnCl2 precursor can be realized simultaneously. Zhao et
al.890 prepared Pt/CeO2/C nanocomposites using H2PtCl6 and
(NH4)2Ce(NO3)6 in the presence of commercial carbon in
mixed solvents of EG and water by one-step pulsed microwave
refluxing at 650 W for 10 min. Pt nanoparticles as well as CeO2
nanoparticles were relatively uniform in size and highly
dispersed on the carbon support. Carbon-supported IrxSey
nanocomposites with different Se/Ir atomic ratios were
synthesized using H2IrCl6 and Na2SeO3 in mixed solvents of
EG and a small amount of water via a microwave-assisted
process. IrxSey nanoparticles were well dispersed on the surface
of the carbon support with a narrow particle size distribution at
y/x ≤ 1/3.887 Ru85Se15 nanoparticles supported on multiwalled
carbon nanotubes were synthesized using RuCl3, Na2SeO3, and
carbon nanotubes in mixed solvents of EG and water by
microwave heating at 900 W for 1.5 min.888 Pt3Te nano-
particles with an average size of ∼2.8 nm well dispersed on
commercial carbon were prepared using H2PtCl6·6H2O and
Na2TeO4·2H2O in mixed solvents of EG and water by
microwave refluxing within a few minutes.889
Chen et al.891 reported the rapid microwave-assisted
synthesis of the magnetic nanocomposite consisting of HAP
ultrathin nanosheets and magnetic Fe3O4 nanoparticles at 120
°C for 30 min. In this method, Ca(CH3COO)2, NaH2PO4·
2H2O, block copolymer PLA−mPEG, and preformed Fe3O4
nanoparticles were used as the starting materials in mixed
solvents of deionized water and EG. For the synthesis of Fe3O4
magnetic nanoparticles, tris(acetylacetonato) iron(III) (Fe-
(acac)3) and tris(acetylacetonato) iron(II) (Fe(acac)2) were
used as the reactants in dibenzyl ether, oleic acid, and ionic
liquid [BMIM][BF4], and the suspension was microwave-
heated to 200 °C and maintained at this temperature for 5 min;
then, the reaction system was heated to 230 °C and maintained
at this temperature for 10 min. The as-prepared nanocomposite
was investigated as the drug nanocarrier using hemoglobin
(Hb) and docetaxel as model drugs. It was found that the
adsorption amount of Hb on the nanocomposite increased with
increasing Hb initial concentration. The release of Hb from the
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Chemical Reviews
nanocomposite was essentially governed by a diffusion process.
The nanocomposite had a good sustained release profile of
docetaxel, and showed the property of pH-responsive drug
release, which can be explained by gradual dissolution of HAP
in a low pH environment. The nanocomposite had a high
biocompatibility and also a high in vitro anticancer effect after
loading docetaxel. Because of the high biocompatibility,
magnetic response property, pH-controlled sustained drug
release, and the ability to enter cells, the as-prepared
nanocomposite is promising for the application in drug
delivery.
Heuser et al.892 reported the microwave-assisted synthesis of
nanoparticles of Fe3O4 or ZnO coated on zeolite A at 150 °C
for 10 min. Glycerin (60% v/v) was added to a FeSO4/zeolite/
NaOH solution to increase the solution viscosity and affect
Fe3O4 nucleation and growth. The microwave irradiation
assisted in displacing either ferrous or zinc ions from the
preloaded zeolite network and increasing the reaction rate.
These experiments showed the ability of using zeolite ion-
exchange as a means of delivering cations in reactions where
the zeolite served as a microreactor. Microwave radiation
increased the ion exchange rate in a controlled manner to
displace ions from the zeolite network to form Fe3O4 or ZnO
by reactions of FeSO4 or Zn(NO3)2 with NaOH. Chang et
al.893 prepared the SnS2/SnO2 nanocomposite adopting SnCl4
and L-cysteine as the reactants in mixed solvents of EG and
water by a microwave-assisted reaction at 700 W for 3 min. The
influence of the molar ratio of SnCl4 to L-cysteine on the
product was investigated. It was found that SnS2/SnO2
nanoparticles were obtained when the molar ratio of SnCl4 to
L-cysteine was 1:2, and nanosheets instead of nanoparticles
were formed at higher content of L-cysteine.
6.1.2. Water/Alcohols. Alcohols are good solvents for
microwave heating, and their abilities to absorb microwaves are
generally better than that of water, as was shown in Table 1.
For example, the loss tangent (tan δ) value of ethanol is 0.941
at 2.45 GHz and 20 °C, much higher than that of water
(0.123). The mixed solvents of water and alcohols will certainly
enhance the abilities to absorb microwaves as compared to that
in the case of using water as the only solvent. Alcohols are
highly miscible with water and are able to form intermolecular
hydrogen bonds with each other and with neighboring water
molecules in solution.25 Because alcohols especially with low
molecular weights have usually relatively low boiling points, the
open reaction systems with mixed solvents of water and
alcohols will allow only low-temperature chemical reactions,
and the solvothermal reactions in closed systems are needed for
relatively high-temperature microwave-assisted synthesis.
A variety of inorganic nanostructures have been prepared by
the microwave-assisted method in mixed solvents of water and
alcohols, including noble metals,896,897 iron oxides,898,899
SnO2,900,901 Eu3+-doped SnO2,902 TiO2,903−906 La3+ and Zr4+
codoped TiO2,907 CuO,908 ZnO,901 SiO2,909 Ni(OH)2,910,911
Co(OH)2,912 Cd(OH)2,913 PbTiO3,271 N-doped titanate,914
Sn2+-doped BaTiO3,915 ZnS:Mn2+,916 CdSe,917 WC,39 YF3 and
lanthanide-doped YF 3 , 918 aluminum hydroxyfluoride, 919
Sn1.24Ti1.94O3.66(OH)1.50F1.42,920 Au/SiO2,921 Ag/mesoporous
SBA-12, 922 Co 3 O 4 /graphene, 923 C/TiO 2 , 924 silica/iron
oxide,925 SiO2-coated Ag,926 SiO2-coated γ-Al2O3,927 TiO2-
coated ZnO,928 Fe3O4/SiO2/NH2,929 TiO2/polystyrene,930 and
polystyrene/CdS.931
Tu et al.896 reported the microwave-assisted preparation of
PVP-stabilized colloidal nanoparticles of a variety of noble
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metals including Pt, Ir, Rh, Pd, and Au in mixed solvents of
methanol and water using a modified domestic microwave
oven. The reactants used were H2PtCl6·6H2O, H2IrCl6·6H2O,
RhCl3·3H2O, H2PdCl4·nH2O, HAuCl4·3H2O, NaOH, and
PVP. The as-prepared colloidal solutions of noble metal
nanoparticles were stable for several months. The colloidal
noble metal nanoparticles synthesized by microwave heating
had smaller relative standard deviations than those prepared by
the conventional oil bath heating, implying a better dispersity of
nanoparticles obtained by microwave heating.
Many papers have been published reporting on the
microwave-assisted synthesis of nanostructured metal oxides
in mixed solvents of water and alcohols. Cao et al.899 reported
the one-step NaCl-assisted microwave-solvothermal synthesis
of monodisperse α-Fe2O3 mesoporous microspheres formed by
oriented assembly of nanocrystals. In this method, Fe(NO3)3·
9H2O was used as the iron source, and PVP acted as a
surfactant in the presence of NaCl in mixed solvents of water
and ethanol. NaCl was found to play an important role in the
formation of monodisperse α-Fe2O3 mesoporous microspheres.
One of the advantages of this method is that the size of α-
Fe2O3 mesoporous microspheres can be adjusted in the range
from ∼170 to ∼260 nm by adjusting the experimental
parameters. α-Fe2O3 mesoporous microspheres exhibited a
high photocatalytic activity in the degradation of salicylic acid.
The combination of the mesoporous structure with mono-
disperse microspheres is beneficial for the enhancement of the
photocatalytic property of α-Fe2O3.
Zhang et al.901 reported the microwave-assisted solvothermal
synthesis of SnO2 or ZnO nanostructured microspheres self-
assembled by nanocrystals using SnCl4·5H 2 O, or Zn-
(CH3COO)2·2H2O, NaOH, ethyl acetate, and CTAB in
mixed solvents of deionized water and methanol at 160 °C
for 30 min. The photocatalytic activity for methyl orange in
aqueous solution was significantly enhanced by simply mixing
as-prepared SnO2 and ZnO nanostructured microspheres as
compared to the single-phase ZnO or SnO2. Birkel et al.900
prepared SnO2 nanocrystals using SnCl4·5H2O and an alkali
(NaOH, KOH, tetramethylammonium hydroxide, or ammo-
nia) in mixed solvents of ethanol and water by a microwave-
assisted solvothermal process at 240 °C for 2 h. The
morphology of the product could be controlled by the use of
different alkalis. SnO2 bundles of nanorods (5−10 nm in
diameter) were obtained in the presence of NaOH, and SnO2
nanocrystals with mixed morphologies of rods, spherical
particles, and plates were obtained using KOH. The use of
tetramethylammonium hydroxide led to the formation of a
mixture of spherical, plate, and rod-like structures; however,
very small nanoparticles were obtained in the presence of
ammonia. Kar et al.902 prepared Eu3+-doped SnO2 nanocrystals
adopting SnCl4·5H2O, Eu(NO3)3·6H2O, and NaOH in mixed
solvents of water and ethanol by microwave heating at 100 °C
for 5 min followed by calcination at 200−800 °C for 1 h. Zhu et
al.908 prepared CuO hierarchical hollow nanostructures
assembled by nanosheets using Cu(NO3)2·3H2O and ammonia
in mixed solvents of n-octanol and water through pulsed
microwave heating at 1000 W for 3 min, and the morphology
and size of building blocks and final products could be tuned by
adjusting experimental parameters.
Wilson et al.903 prepared anatase TiO2 nanoparticles with
sizes of 3−5 nm using titanium isopropoxide and HNO3 in
mixed solvents of water and isopropanol by microwave-
solvothermal treatment for 5−10 min. Periyat et al.904 prepared
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spherical aggregates of mesoporous nanocrystalline TiO2 using
titanium butoxide in mixed solvents of deionized water and an
alcohol (isopropanol, ethanol, or butanol) by microwave
heating at a power of 300 W for 2 min. The as-prepared
materials possessed high specific surface areas up to 240 m2 g−1,
which are higher than those of similar traditional sol−gel
prepared or commercial samples. Wang et al.905 prepared
porous anatase TiO2 spheres using titanium glycolate
precursors (obtained by an EG-mediated sol−gel process) in
mixed solvents of ethanol and water by microwave heating at
150 °C for 10 min. The effects of experimental conditions on
the formation of titanium glycolate precursors and final TiO2
spheres were investigated. Zhu et al.906 prepared TiO2 porous
hollow microspheres formed by self-assembly of nanosized
building blocks using tetrabutyl titanate as the titanium source
in mixed solvents of ethanol and deionized water by
microwave-assisted solvothermal treatment at 180 °C for 1 h.
The continuous flow microwave reactors have also been used
for the synthesis of metal oxide nanostructures in mixed
solvents of water and alcohol. Corradi et al.909 prepared SiO2
spherical nanoparticles from the hydrolysis and condensation of
tetraethyl orthosilicate (TEOS) in mixed solvents of methanol
and water by using a continuous flow microwave synthesis
process. The flow rate was varied from 43 to 101 mL min−1.
The mean particle diameter became smaller than 50 nm as the
residence time was decreased by increasing the flow rate to 101
mL min−1.
Zhu et al.271 prepared PbTiO3 nanowires with diameters of
40−60 nm and lengths up to several micrometers and the
aspect ratio close to 90 using Pb(CH3COO)2·3H2O, Ti-
(OC4H9)4, and KOH in mixed solvents of water and ethanol by
a microwave-solvothermal process at 200 °C for 90 min. The
as-prepared nanowires tended to grow into a regular structure
with parallel arrangement along their long axis in the [001]
direction. Nitrogen-doped titanate nanotubes were prepared
using preformed titanate nanotubes dispersed in mixed solvents
of ethanol and water containing NH4Cl by a microwave-
solvothermal process at 130 °C for 2 h.914 Sn2+-doped BaTiO3
nanopowder was synthesized using BaCl2, SnCl2·2H2O, Ti(i-
C3H7O)4, and KOH in mixed solvents of water and i-propanol
by the microwave-assisted solvothermal method at 200 °C for 1
h. The particle sizes of Ba1−xSnxTiO3 were 20−40 nm and
increased with increasing amount of doped Sn2+.915
Metal hydroxide nanostructures have also been prepared by
the microwave-assisted method in mixed solvents of water and
alcohols. Xu et al.910 prepared nanostructured flower-like α-
Ni(OH)2 architectures consisting of aggregated nanoflakes
using Ni(NO3)3·6H2O and urea in mixed solvents of distilled
water and ethanol by the microwave-assisted solvothermal
method at 90 °C for 15 min. The nanoflakes as the building
blocks were built up from many nanocrystals with diameters of
2−3 nm. The as-prepared α-Ni(OH)2 flower-like nanostruc-
tures had a higher electrochemical activity in the electro-
chemical reduction of O 2 as compared to α-Ni(OH) 2
synthesized by the conventional solvothermal method. Ni-
(OH)2 flower-like architectures assembled with nanosheets
with thicknesses of 10−20 nm were synthesized using
Ni(NO3)2·6H2O, urea, NH3·H2O, and PEG in mixed solvents
of water and ethanol through the microwave-assisted
solvothermal method at 160 °C for 30 min.911 The micro-
wave-assisted synthesis of Co(OH)2 nanostructures was
reported using CoCl2·6H2O and HMTA in mixed solvents of
water and ethanol at 90 °C for 1−4 min.912 Ultralong and
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flexible necklace-like nanostructures of Cd(OH) 2 were
prepared in the n-octanol/aqueous liquid system by microwave
heating, and a mechanism based on the synergistic effect of
bubble-template and interface-assistance was proposed.913
Nanostructured metal chalcogenides have also been prepared
in mixed solvents of water and alcohols by the microwave-
assisted method. Ayele et al.917 developed the low-temperature
microwave-assisted synthesis of CdSe quantum dots with
tunable sizes without adopting the hot injection technique. In
their synthesis, Cd(CH3COO)2·2H2O, Na2SeSO3, and NaOH
were used as reactants, a mixture of ethanol and deionized
water was used as the solvent, and oleic acid was used as a
capping ligand. By simply adjusting the experimental conditions
such as temperature, time, and microwave power, CdSe
quantum dots with sizes ranging from 2.3 to 2.8 nm were
obtained.
The microwave-assisted method has been proven to be
successful for the preparation of nanostructures of many other
compounds in mixed solvents of water and alcohols. YF3 and
lanthanide-doped YF3 nanocrystals were prepared in mixed
solvents of ethanol and water by the microwave-assisted
approach at 90 W for 15 min. The as-prepared nanocrystals
had diameters of ∼6−10 nm, and these nanoparticles
aggregated to form bigger assemblies with diameters of ∼40−
60 nm. The as-prepared YF3 nanocrystals could well disperse in
water, forming a stable and transparent colloidal solution.918
Dambournet et al.919 reported the two-step microwave-assisted
solvothermal synthesis of platelet-shaped aluminum hydroxy-
fluorides derived from β-AlF3 using Al(NO3)3·9H2O and HF in
mixed solvents of water and isopropanol at 100 °C for 10 min
and then at 160 °C for 2 h.
The surface modification of various nanoparticles with silica
was investigated for biomedical applications. However, silica
encapsulation through the conventional methods requires long
reaction times (hours to days). Bahadur et al.921 reported rapid
one-step microwave-assisted preparation of silica-coated gold
(Au/SiO2) nanoparticles with tunable silica shell thickness and
surface functionalization (Figure 25). Figure 25a shows the
Figure 25. TEM micrographs: (a) uncoated Au nanoparticles; (b)−
(h) Au@SiO2 nanoparticles with different silica shell thicknesses
prepared by the microwave-assisted method at different TEOS
concentrations: (b) 1 mM, (c) 2 mM, (d) 3 mM, (e) 5 mM, (f) 10
mM, (g) 15 mM, and (h) 20 mM. [H2O] = 11 M, [NH3·H2O] = 0.8
M. Reprinted with permission from ref 921. Copyright 2011 Elsevier
B.V.
TEM micrograph of uncoated Au nanoparticles prepared by the
citrate reduction method, and the sizes of uncoated Au
nanoparticles were uniform with an average diameter of ∼16
nm. Silica coating was carried out by microwave heating a
reaction system containing Au nanocrystals, TEOS, and
ammonia in mixed solvents of water and ethanol at 50 °C for
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5 min. Au/SiO2 nanoparticles with a wide range of silica shell
thicknesses (5−105 nm) were prepared within 5 min of
microwave irradiation by only changing the concentration of
TEOS. The size uniformity and monodispersity of Au/SiO2
nanoparticles were found to be better as compared to the
product prepared by the conventional method. The microwave
irradiation significantly reduced the preparation time (within 5
min) as compared to that of the conventional methods (hours
to days). TEM micrographs of Au@SiO2 nanoparticles with
different silica shell thicknesses prepared by the microwave-
assisted method (Figure 25b−h) show that almost all of the
nanoparticles contained a single core of Au nanoparticle (∼16
nm) in the center. The as-prepared Au/SiO2 nanoparticles were
further functionalized with amino, carboxylate, and alkyl
groups. Park et al.925 demonstrated that uniform and spherical
silica encapsulation of magnetic iron oxide nanoparticles could
be achieved within 10 min via microwave irradiation after
tetramethylammonium hydroxide-mediated phase transfer of
monodisperse magnetic nanoparticles from the organic phase
(2-propanol) to the water phase using TEOS.
Siddiquey et al.927 prepared SiO2-coated γ-Al2O3 nano-
particles by microwave heating. They first obtained the ethanol
dispersion of γ-Al2O3 nanoparticles with diameters of ∼30 nm
by the ball-milling technique. The γ-Al2O3 dispersion together
with TEOS and aqueous ammonia in mixed solvents of ethanol
and water then were heated by microwaves at 70 °C for 2 min
in an open system, leading to rapid coating of γ-Al2O3
nanoparticles with a homogeneous silica shell with the
thicknesses of ∼3−4 nm. This work demonstrates that the
microwave heating can not only enhance chemical reactions,
but also realize the homogeneous coating on nanoparticles.
Thus, microwave heating is suitable for in situ synthesis of the
core/shell nanostructures. A similar method was also applied to
the coating of SiO2 on Ag nanoparticles using preobtained
colloidal Ag, TEOS, and dimethylamine in mixed solvents of
water and ethanol by microwave heatng at 50 °C for 2 min.926
The nanocomposite of amorphous TiO2 layer (6−10 nm)
coated on ZnO was prepared using titanium tetra-n-butoxide as
the titanium source and commercial ZnO nanoparticles in
mixed solvents of ethanol and water by the rapid microwave-
assisted method at 70 °C for 2 min.928 Stutz et al.929 prepared
Fe3O4/SiO2/NH2 core−shell nanoparticles by a three-step
microwave-assisted route. They first prepared Fe3O4 nano-
particles using iron(III) acetylacetonate in benzyl alcohol under
inert atmosphere by microwave heating at 170 °C for 12 min.
In the next steps, they prepared Fe3O4/SiO2 and Fe3O4/SiO2/
NH2 core/shell nanoparticles using dispersed Fe3O4 or Fe3O4/
SiO2, TEOS, and ammonia in mixed solvents of ethanol and
water by microwave heating at 60 °C for 3 min.
A combined procedure of sol−gel and microwave-assisted
emulsion polymerization has been developed to prepare TiO2/
polystyrene core−shell nanospheres with TiO2 nanoparticle as
the core and polystyrene as the shell. Ti(OC4H9)4 and NaOH
were used as the reactants in mixed solvents of water and
ethanol by microwave heating at 40 °C for 40 min. The
resulting TiO2 colloid was heated to 70 °C under nitrogen
atmosphere, and then sodium dodecyl sulfonate, ammonium
persulfate, and styrene monomer were added to initiate the
emulsion polymerization on the surface of TiO2 colloidal
nanoparticles. It was found that the diameter of the TiO2/
polystyrene core−shell nanospheres could be regulated by the
concentration of styrene monomer.930 Polystyrene/CdS core−
shell nanostructures were fabricated using CdCl2·2.5H2O,
6521
Review
thioacetamide, and PVP in the presence of polystyrene
microspheres in mixed solvents of deionized water and alcohol
under microwave irradiation at 70 °C for 1.5 h.931
6.1.3. Water/N,N-Dimethylformamide. The mixed sol-
vents of water and N,N-dimethylformamide (DMF) have been
less reported for the microwave-assisted preparation of
inorganic nanostructures. Xu et al.932 reported the micro-
wave-solvothermal synthesis combined with thermal treatment
for the preparation of Y4Al2O9 hierarchically nanostructured
microspheres assembled with nanosheets. First, the microwave-
assisted solvothermal method was used to prepare the
precursor using Y(NO3)3 and Al(NO3)3 at 200 °C for 1 h in
mixed solvents of water and DMF without any surfactant (pH
∼9 adjusted by aqueous ammonia). The thermal treatment of
the precursor at 900 °C in air for 2 h then was performed to
obtain Y4Al2O9 hierarchically nanostructured microspheres, and
the morphology of the precursor could be well preserved. The
photocatalytic activity of as-prepared Y4Al2O9 hierarchically
nanostructured microspheres over phenol was investigated, and
the degradation rate of phenol reached 91.2% in a time period
of 4 h.
6.1.4. Water/1,2-Ethylenediamine. The mixed solvents
of water and 1,2-ethylenediamine have also been adopted for
the microwave-assisted preparation of inorganic nanostructures.
Apte et al.933 prepared Mn3O4 nanostructures using manganese
nitrate in mixed solvents of water and ethylenediamine by
microwave heating. The nanostructures were mostly spherical/
cubic in shape and had sizes in the range of 10−50 nm; Mn3O4
nanorods with diameters of 9−10 nm were also obtained. Yan
et al.446 synthesized α-Fe2O3 spindle-like structures using
Fe(NO3)3·9H2O in mixed solvents of ethylenediamine and
distilled water by the microwave-assisted solvothermal method
at 500 W for 50 min.
Limaye et al.934 prepared ZnS nanorods with diameters of
∼50−100 nm using ZnCl2 and thiourea in mixed solvents of
water and ethylenediamine by microwave heating. It was
revealed that the microwave refluxing time played an important
role in determining the diameter of the nanorods. Li et al.935
synthesized ZnxCd1−xS nanorods with diameters of ∼10 nm
using a preformed Zn−Cd precursor in mixed solvents of
ethylenediamine and water by microwave heating at 140−160
°C for 10 min. Zn0.28Cd0.72S exhibited the best photocatalytic
activity for the degradation of methyl orange under visible light
with a conversion ratio up to 96% after 6 h irradiation, which
was higher than that of the sample prepared by the
conventional solvothermal method.
Ma et al.936 synthesized SrCO3 one-dimensional nanostruc-
tures assembled from nanocrystals using Sr(NO 3 ) 2 ,
(NH4)2CO3, ethylenediamine, and water by the microwave-
assisted solution method at 90 °C. The experiments showed
that the microwave heating time played an important role in the
size and morphology of SrCO3. Zn2GeO4 nanorod bundles
consisting of nanorods of 40−70 nm in diameter were prepared
using Zn(CH3COO)2·2H2O and GeO2 in the presence of PEG
in mixed solvents of water and ethylenediamine via the
microwave-assisted approach at 170 °C for 15 min.937
6.1.5. Other Binary Solvents. A variety of other binary
solvents have also been applied to the microwave-assisted
preparation of inorganic nanostructures. Examples for the
microwave-assisted preparation of elemental nanostructures are
discussed below. Doolittle et al.938 adopted a water−sodium
bis(2-ethylhexyl) sulfosuccinate (AOT)-heptane reverse micelle
system for the preparation of Au nanoparticles by hydrazine
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reduction of HAuCl4 under microwave radiation at 300 W,
typically for 2 min. Chen et al.939 prepared Pd nanoparticles via
thermal decomposition of palladium acetate in the presence of
an alkali in methyl isobutyl ketone and butanol under
microwave irradiation for 1 min. The average diameters of Pd
nanoparticles increased from 30 to 40 nm with the increase in
the concentration of palladium acetate, and the as-prepared Pd
colloidal nanoparticles were agglomerates from hundreds of
smaller nanoparticles with sizes of 3−4 nm. Tong et al.940
prepared 28−81 nm Pd pompon-like nanostructures formed by
self-assembly of nanoparticles with an average size of ∼2.4 nm
by thermal decomposition of palladium acetate in methyl
isobutyl ketone and a small amount of EG under microwave
irradiation at 900 W for 1 min. The sizes of Pd pompon-like
nanostructures could be controlled by adjusting the concen-
tration of palladium acetate. Rapid microwave-assisted thermal
reduction of graphene oxide to graphene was achieved in mixed
solvents of N,N-dimethylacetamide and water at the temper-
ature up to 165 °C for 1−10 min.941
Nanostructured metal oxides have been successfully prepared
by the microwave-assisted method in a variety of binary
solvents. For example, microporous SnO2 nanostructures were
prepared using SnCl4·5H2O amd CTAB in mixed solvents of
water and ethanolamine via microwave heating at 160 °C for 10
min, and different SnO2 nanostructures could be obtained by
adjusting the concentration of CTAB.942 ZnO nanoparticles
and nanorods were synthesized from the reaction between
Zn(NO3)2·6H2O and NaOH in water and PEG with low
molecular weights under 180 W microwave irradiation for 30
min.943 ZnO micro- and nanostructures with a variety of
morphologies were synthesized using Zn(NO3)2·6H2O, pyr-
idine, and water by the microwave-assisted method at 90 °C for
10 min. The pyridine had a significant influence on the
morphology of ZnO. Various morphologies of ZnO (hexagonal
columns, linked hexagonal needles, hollow structures, and
hexagonal nanorings) were obtained by adjusting the
concentration of pyridine. The effects of other alkaline additive
(aniline and triethanolamine) on the morphology of ZnO were
also investigated.944 α-Fe2O3 nanoparticles were synthesized
using FeCl3 in mixed solvents of absolute ethanol and acetic
acid by the combination of microwave irradiation and
esterification at 150 °C for 15 min. In this method, water
produced by the esterification between ethanol and acetic acid
leads to the forced hydrolysis of Fe3+ ions. Microwave
irradiation greatly promoted the growth of α-Fe2O3 nano-
particles as compared to the conventional solvothermal
approach, agitation could ensure the formation of pure
hematite phase, and the akaganeite phase was formed without
stirring.945 By using a similar method, TiO2 nanoparticles with
sizes of ∼9−12 nm were obtained.946 Szeifert et al.947 prepared
highly dispersible anatase TiO2 nanoparticles with sizes of ∼3
nm using TiCl4 in mixed solvents of tert-butyl alcohol and
toluene. Microwave heating could enhance the crystallinity of
the nanoparticles and drastically shorten the reaction time to
less than 1 h at a temperature as low as 50 °C. Parmar et al.948
reported the rapid (10 min) microwave-solvothermal synthesis
of TiO2 nanorice nanoparticles (6−15 nm wide, 30−100 nm
long) using Ti-isopropoxide in mixed solvents of acetylacetone
and deionized water (pH ∼11.7 adjusted by 30% ammonia) at
180 °C. In addition, the as-synthesized TiO2 nanorice
nanoparticles showed a high stability against annealing
treatment, retaining high surface area and large pore volume.
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Review
Nyutu et al.949 produced multigram quantities of cryptome-
lane-type manganese oxide (K-OMS-2) nanostructured materi-
als in the size range of 4−20 nm and with high surface areas up
to 227 m2 g−1 via an open-vessel microwave-refluxing route in
aqueous and nonaqueous mixed solvents. The solvents used
were dimethyl sulfoxide, DMF, EG, propylene glycol, sulfolane,
dimethylacetamide, ethanol, N-methyl pyrrolidone, and ethyl
acetate. The OMS-2 nanofiber diameter could be controlled by
varying the amount of the cosolvent or type of the cosolvent.
Opembe et al.950 reported the continuous flow microwave
synthesis of cryptomelane-type K-OMS-2 nanofibers with a
specific surface area of 213 m2 g−1 in the mixed aqueous/
organic solvent system. Panda et al.951 reported the rapid
microwave-assisted production of nanorods, nanowires, and
nanoplates of rare earth oxides (M2O3, M = Pr, Nd, Sm, Eu,
Gd, Tb, Dy). Metal acetate or acetylacetonate was used as the
starting reagent in oleic acid and oleylamine, and the resulting
solution was placed in a microwave oven with the power set to
70% of 650 W and operated in 3 min cycles (on for 2.5 min, off
and stirring for 0.5 min). The uniformity of the nanorods and
nanowires was demonstrated from their spontaneous assembly
into highly ordered 2-D superstructures.
Nanostructured metal chalcogenides have been successfully
prepared by the microwave-assisted method in a variety of
mixed solvents. Caponetti et al.952 adopted microwave
irradiation in a water−sodium bis(2-ethylhexyl) sulfosucci-
nate−heptane microemulsion system to prepare CdS nano-
particles. The reaction was carried out in an open system, and
the temperature was maintained at 35 °C by using a low
microwave power ranging between 22 and 30 W. Under these
circumstances, water was selectively driven off the aqueous core
of reverse micelles, and, as a consequence, small, crystalline, and
anhydrous CdS nanoparticles could be obtained. It was
observed that microwave-irradiated nanoparticles grew faster
and their size reached a constant value, and the final mean
particle diameter was 2.7 nm, smaller than that observed in a
nonirradiated sample. Shinde et al.953 prepared CdS nanorod
bundles as well as sea urchin-like and starfish-like hierarchical
nanostructures using Cd(CH3COO)2 and thiourea in dieth-
ylene triamine and water by the microwave-assisted method at
140 °C for 10 min. Amalnerkar et al.954 reported the
microwave-assisted solvothermal synthesis of hierarchical CdS
nanostructures including entangled nanorods, nanosticks, and
nanoflowers using Cd(CH3COO)2 and thiourea in binary
solvents of diethylenetriamine and deionized water typically
within 5 min. Patra et al.955 reported a microwave-assisted route
to nanoflakes and dendrite-type β-In2S3 in high yield (>97%)
using InCl3 and thiourea in mixed solvents of EG and PEG-400,
and the length and width of the resulting nanoflakes were in the
range of 70−600 and 4−10 nm, respectively. Yan et al.956
prepared amorphous α-Ag2S nanowires using AgNO3 in
thioglycolic acid and water under microwave irradiation at
various powers for 3 or 5 min. Wang et al.957 reported a two-
phase microwave-assisted synthesis of Cu2S nanocrystals in the
toluene−water system using CuSO4 and dodecanethiol as the
reactants at 190 °C for 4 h under a dynamic mode with a
microwave power output of 125 W. The formation of Cu2S
nanocrystals was strongly correlated with the reaction temper-
ature and time. The size of Cu2S nanocrystals could be
controlled from 3 to 8 nm by varying the concentration of
alkyl-thiol. Panigrahi et al.958 prepared WS2 nanowires using
tungstic acid and sulfur in monoethanolamine and water
through a microwave-assisted route at 800 W for 5−6 min in
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Chemical Reviews
cycles of 30 s. Acidification of the precursor solution yielded
amorphous precipitate, which led to the formation of WS2
nanowires with diameters of ∼5−10 nm when heated at 750 °C
under argon atmosphere for 1.5 h. CuInS2 nanoparticles were
synthesized by decomposition of a single source precursor
(Ph3P)2Cu(μ-SEt)2In(SEt)2 in dioctyl phthalate or benzyl
acetate in the presence of 1,2-ethanedithiol via microwave
irradiation at a reaction temperature as low as 100 °C and
reaction times as short as 30 min. The particle sizes were 1.8−
10.8 nm as reaction temperatures were varied from 100 to 200
°C with good size control and high yield (up to 95%).959
Sliem et al.960 reported the synthesis of PbSe nanocrystals by
the conventional hot injection process and also microwave
irradiation using lead acetate, selenourea, and oleic acid in
phenyl ether and DMF. They investigated the shape evolution
of PbSe nanocrystals during microwave synthesis. The
mechanism of morphology evolution from spherical to cubic
shape was discussed. They proposed that the formation of PbSe
nanocubes is attributed to the higher growth rate in the [111]
direction as compared to that in the [100] direction. Han et
al.961 reported the microwave-assisted synthesis of ZnSe
nanostructures with different morphologies including nano-
particles, rice-like nanocrystals, and rods using a solution of
Zn(CH3COO)2·2H2O in octylamine or octyldecylamine and a
solution of Se in Tri-n-butylphosphine at 180 °C for 1−20 min.
Panda et al.962 reported the rapid microwave-assisted synthesis
of aligned nanorods and nanowires of ZnS, ZnSe, CdS, and
CdSe in a mixture of alkylamines (C6−C18) and DMF. For the
synthesis of sulfides, a single precursor metal ethyl xanthate was
used; and for selenides, a mixture of metal acetate and
selenourea precursors was used.
Nanostructured metal fluorides have also been successfully
prepared by the microwave-assisted method in a variety of
mixed solvents. A variety of monodisperse GdF3:Yb,Er
upconversion nanocrystals with different shape, size, and
dopants were synthesized by the microwave-assisted method
at 290 °C for 10 min. In this method, lithium trifluoroacetate
(TFA), gadolinium TFA, ytterbium TFA, and erbium TFA
were used as the reactants in a 1:1 (v:v) mixture of oleic acid
and octadecene in nitrogen atmosphere. In addition to
monodisperse spherical nanoparticles, rhombic-shaped slices
that showed a tendency for self-assembly into stacks were also
obtained.963 Wang et al.964 synthesized monodisperse NaYF4
nanocrystals using corresponding metal trifluoroacetates in
mixed solvents of 1-octadecene and oleic acid by the
microwave-solvothermal method at 290 °C for 5 min. Doping
with Li+ ions resulted in a significant increase in upconversion
efficiency and a transition from cubic to tetragonal crystal
lattice. AYF4:Yb,Er (A = Na, Li) nanocrystals were synthesized
in mixed solvents of 1-octadecene and oleic acid using a
microwave-assisted process at 290 °C for 10 min.965 It was
found that the size of the nanocrystals could be controlled by
adjusting the growth time, and the morphology of the
nanocrystals could be controlled by the reactant concentration
and composition. Low reactant concentrations resulted in
monodisperse spherical nanocrystals; however, at high
concentrations, nanocrystals grew into flowers when the
crystallographic lattice was cubic, into wires at a Na/Li ratio
of 1:4, and into rhombic shape for LiYF4:Yb,Er nanocrystals.
KMgF3 nanocrystals were synthesized via the thermolysis of
metal trifluoroacetate precursors in mixed solvents of oleic acid
and oleylamine under microwave irradiation at 290 °C for 30
min. The crystal phase and shape of nanocrystals could be
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controlled by the variation of the ratio of oleic acid/oleylamine,
resulting in the formation of near-spherical nanoparticles, and
nanoplates of cubic-phased KMgF3, as well as nanorods of
tetragonal-phased MgF2. Tb3+-doped KMgF3 nanocrystals were
also prepared by this method, and they exhibited a strong green
emission.966
Liu et al.967 reported that photoluminescent carbon nitride
dots could be prepared using CCl4 and 1,2-ethylenediamine as
both reactants and solvents by a simple heat treatment-based
strategy. The formation of carbon nitride dots was attributed to
the polymerization of CCl4 and 1,2-ethylenediamine under
refluxing by microwave heating or solvothermal heating. The
as-prepared carbon nitride dots exhibited a strong fluorescence.
Various nanocomposites can also be prepared by the
microwave-assisted method in a variety of mixed binary
solvents. Campelo et al.922 prepared nanocomposites of Au
or Pd nanoparticles/mesoporous SBA-12 using gold bromide
or palladium acetate in mixed solvents of ethanol and acetone
by microwave heating at 100−140 °C for different times (2, 5,
10, and 20 min). The metal nanoparticles had different sizes
depending on the metal and the time of microwave irradiation.
Herring et al.968 prepared ZnO nanopyramids supported on
reduced graphene oxide nanosheets by microwave heating
Zn(CH3COO)2 and graphene oxide in a mixture of oleic acid
and oleylamine. Highly active Pt/TiO2/C nanocomposite was
synthesized in mixed solvents of EG and isopropyl alcohol by a
microwave-assisted process.969
Herring et al.970 reported a fast one-pot microwave-assisted
synthesis route to Au/ZnO hybrid hexagonal nanopyramids by
sequential homogeneous−heterogeneous nucleation steps. The
rapid decomposition of Zn(CH3COO)2 by microwave heating
in the presence of a mixture of oleic acid and oleylamine
resulted in the formation of hexagonal ZnO nanopyramids. In
the presence of Au ions, the initially formed Au nanocrystals
acted as heterogeneous nuclei for the nucleation and growth of
ZnO nanopyramids. Using preformed Au nanoparticles instead
of Au ions resulted in a narrow size distribution of uniform Au/
ZnO nanopyramids, each consisting of a gold nanoparticle
embedded in the center of the hexagonal base of the ZnO
nanopyramid. ZnO did not form by microwave heating the
reaction mixture for 10 min with powers ranging from 100 to
500 W, and the first sign of ZnO growth was observed after 10
min of microwave heating at a power of 600 W (126 °C). ZnO
spindles began to grow from gold nanoparticles resulting in
Au−ZnO nanocomposites that consisted of a spherical gold
nanoparticle attached to a small ZnO rod. As the microwave
power was increased to 700 W (149 °C), the ZnO spindles
attached to gold nanoparticles increased in size. By increasing
the microwave power to 800 W (160 °C), the ZnO spindles
began to encapsulate the gold nanoparticle in the center of the
hexagonal base, and the development of the ZnO nanopyramid
could be clearly observed. Further increase of the microwave
power to 900 W (184 °C) resulted in a sudden increase in the
number density of the Au/ZnO nanostructures, and most of
the nanopyramids appeared to be fully developed. Finally, with
full microwave power of 1000 W (214 °C), well-defined
hexagonal pyramids, with each pyramid containing a single Au
nanoparticle in the center of its hexagonal base, were formed as
shown in Figure 26.
Bensebaa et al.971 prepared Pt−Ru nanoparticles with an
average size of 2.8 nm stabilized within a conductive polymer
matrix polypyrrole di(2-ethylhexyl) sulfosuccinate by micro-
wave refluxing heating at 163 °C for 3 min, and H2PtCl6, RuCl3,
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Figure 26. TEM micrograph of Au/ZnO nanostructures obtained
from a reaction mixture containing 0.05 M Zn(CH3COO)2, 0.5 mL
solution of preformed Au nanoparticles, and 1:2 molar ratio of oleic
acid/oleylamine after 10 min microwave irradiation at a power of 1000
W (214 °C). Reprinted with permission from ref 970. Copyright 2011
American Chemical Society.
and polypyrrole di(2-ethylhexyl) sulfosuccinate were used as
the starting materials in methanol and EG. Kate et al.972
synthesized the polypyrrole/Ag nanocomopposites under
microwave irradiation based on interfacial polymerization at a
water/chloroform interface using pyrrole and AgNO3 solutions
at 20% microwave power of 800 W for 1, 2, and 3 min. Pyrrole
was partially dissolved in chloroform and AgNO3 was
completely dissolved in distilled water, and the reaction
proceeded at the water/chloroform interface, leading to the
formation of Ag nanoparticles with sizes of ∼20 nm dispersed
in the polypyrrole matrix.
6.2. Ternary and Multinary Solvent Systems
In recent years, some researchers have adopted ternary and
multinary solvent systems for the microwave-assisted prepara-
tion of a variety of inorganic nanostructures, including Au,973
Ag,974 ZnO,975 α-Fe2O3,976 γ-Fe2O3,977 Fe3O4,978 Co3O4,979
TiO2,980 CeO2,981 ZrO2,982 ZnS,983 Ag2S,974 CdSe,984,985
CdTe, 986 pnictogen chalcogenide, 987 SrTi 1−x Cr x O 3 , 988
MFe2O4 (M = Ni, Co, Mn),977 AlOOH,989 AlOOH:Tb3+,990
aluminum hydroxyfluoride,991 NaGdF4:Ln3+ (Ln = Yb, Er/Tm/
Ho),992 Eu3+-doped HAP,993 zeolite,994 Au/carbon nano-
tubes,995 TiO2/graphene,996 Pt/WO3/C,997 Pt/polypyrrole,998
La2O3/BaCO3,999 CdSe/graphene,1000 CdSe/ZnS,1001,1002 and
ZnO/ZnS/γ-Fe2O3.1003
For the microwave-assisted preparation of metal nanostruc-
tures in ternary and multinary solvent systems, two examples
are discussed below. Mohamed et al.973 reported the fast one-
pot microwave-assisted preparation of Au nanoparticles with
different shapes capped with a mixture of oleylamine and oleic
acid. In this method, an appropriate amount of HAuCl4 in HCl
solution was mixed with oleylamine and oleic acid, and the
reaction system was microwave heated for only ∼1 min. The
size and morphology of the nanocrystals could be tailored by
varying the ratio of oleylamine to oleic acid, microwave heating
time, and concentration of HAuCl4. Pure oleylamine led to the
formation of only spherical Au nanoparticles, and addition of
oleic acid increased the growth rate and enhanced the
formation of anisotropic shapes. Figure 27 shows the TEM
micrographs of Au nanoparticles prepared in the presence of
oleylamine and in a 1:1 ratio of oleylamine to oleic acid,
indicating that in both cases the resulting Au nanoparticles were
spherical but exhibited clearly different sizes. The average sizes
of the nanoparticles prepared in pure oleylamine and in a 1:1
ratio of oleylamine to oleic acid were ∼8.0 ± 1.0 and 15.0 ± 2.0
nm, respectively. Gao et al.974 reported the preparation of
hexagonally arranged spherical Ag nanocrystals by one-step
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Figure 27. TEM micrographs of Au nanoparticles prepared using
oleylamine (a) and in 1:1 ratio of oleic acid/oleylamine (b). Reprinted
with permission from ref 973. Copyright 2010 American Chemical
Society.
microwave-assisted solvothermal interface reaction at 160−170
°C for 3 h using AgNO3, dodecylthiol, EG, and toluene. The
ratio of EG/dodecylthiol had an effect on the morphology and
arrangement of the obtained Ag nanoparticles. At a low volume
ratio, Ag nanocrystals with a rectangular shape arranged in
orthogonal arrays could be observed.
Metal oxide nanostructures have also been prepared by the
microwave-assisted method in ternary and multinary solvent
systems. Erten-Ela et al.975 prepared ZnO nanorods using
Zn(CH3COO)2·2H2O and NaOH in mixed solvents of water,
PEG-400, and absolute ethanol by microwave heating at 140 °C
for 30 min. α-Fe2O3 nanocubes were prepared by thermal
decomposition of iron oleate complex in mixed solvents of oleic
acid, triethylene glycol, ethanol, and water via the microwave-
assisted solvolthermal method at 400 W for 6 min, followed by
the Ostwald ripening process, and the primary nanoparticles
synthesized by microwave heating were low crystalline with an
average diameter of ∼6 nm.976 Co3O4 nanocubes with sizes of
∼20 nm were prepared using Co(NO3)2·6H2O and sodium
oleate in mixed solvents of ethanol, hexane, and deionized
water by the microwave-assisted solvothermal method at 200
°C for 20 min.979 Hierarchical nanostructures of TiO2 were
prepared using TiF4, urea, and CTAB in mixed solvents of
water, cyclohexane, and 1-pentanol by the microwave-assisted
method at 120 °C for different time periods.980 CeO2
nanoparticles, nanocubes, and nanorods were synthesized
using Ce(NO3)3 in mixed solvents of water, EG, oleic acid,
and tert-butylamine by microwave heating for 2−30 min, and
the shape of CeO2 nanostructures could be adjusted simply by
varying the microwave irradiation time.981 ZrO2 nanoparticles
were synthesized from the hydrolysis and condensation of tetra-
n-propylzirconate in mixed solvents of ethanol, caproic acid,
and water by a continuous microwave synthesis process.982
Sulaeman et al.988 reported the microwave-assisted solvo-
thermal synthesis of Cr-doped SrTiO3 (SrTi1−xCrxO3, x = 0−
0.2) nanoparticles (15−20 nm) using SrCl2·6H2O, Cr(NO3)3·
9H2O, Ti(OC3H7)4, and KOH in mixed solvents of water, 2-
propanol, methanol, and oleic acid at 200 °C for 3 h. Baruwati
et al.977 synthesized MFe2O4 (M = Ni, Co, Mn) and γ-Fe2O3
nanoparticles with sizes of 5−10 nm at the water−toluene
interface in the presence of oleic acid under the conventional as
well as microwave hydrothermal conditions using nitrate or
chloride salts. AlOOH hierarchically nanostructured micro-
spheres constructed by nanosheets were prepared by the
microwave-assisted solvothermal method using AlCl3·6H2O,
NaOH, and CTAB in a mixture of deionized water, methanol,
and ethyl acetate at 160 °C for 30 min. γ-Al2O3 hierarchically
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nanostructured microspheres were obtained by heating AlOOH
hierarchically nanostructured microspheres to 500 °C in air,
and the morphology could be well preserved during the thermal
transformation process.989 AlOOH:Tb3+ microspheres con-
structed by nanosheets were prepared using AlCl3·H2O,
Tb(NO3)3·H2O, NaOH, and CTAB in a mixture of deionized
water, methanol, n-butyl alcohol, and ethyl acetate via the
microwave solvothermal approach at 160 °C for 30 min.990
Dambournet et al.991 synthesized pyrochlore-type aluminum
hydroxyfluoride nanoparticles with an average size of 12 nm
using a microwave-solvothermal process. The reactants used in
the synthesis were Al(III) isopropoxide and HF in mixed
solvents of isopropanol, ether, and distilled water. In the first
step, a temperature of 200 °C was rapidly reached by keeping
the microwave power at 300 W; thereafter, the temperature was
kept at 160 °C for 1 h. The optimization of the crystallite size
and surface area of the product was performed by varying
experimental parameters including the nature of the aluminum
precursor, choice of solvents, and addition of a small amount of
ether.
Wang et al.992 adopted the microwave-solvothermal method
for the rapid synthesis of nanocrystals of lanthanide-doped
hexagonal phase NaGdF4:Ln3+ (Ln = Yb, Er/Tm/Ho) with
multicolour upconversion luminescence and paramagnetic
properties. LnCl3, NaF, and NaOH were used as the starting
reagents in mixed solvents of deionized water, oleic acid, and
alcohol. The shape of the nanocrystals could be manipulated
from rod-like to spherical just by tuning the initial
concentration of reactants. The product obtained at 160 °C
for 5 min was relatively uniform nanorods with the average
sizes of 76.4 ± 1.3 nm in length and 17.1 ± 0.6 nm in diameter.
When the reaction temperature was kept at 160 °C and the
reaction time changed, the as-prepared product exhibited a
uniform rod-like morphology, while the aspect ratio of
nanorods varied obviously with the reaction time. For example,
the average length increased from 76.4 to 121.5 nm when
prolonging the holding time from 5 to 90 min. Yang et al.993
prepared Eu3+-doped HAP nanostructures including nanorods
and nanoparticles using Eu(NO 3 ) 3 , Ca(NO 3 ) 2 ·4H 2 O,
(NH4)2HPO4, and CTAB in mixed solvents of n-butanol, n-
octane, and water via a microemulsion-mediated microwave-
assisted process, and the morphology of the product could be
adjusted by altering the pH value.
Various nanocomposites have been successfully prepared by
the microwave-assisted method in ternary and multinary
solvent systems. For example, the microwave-assisted micro-
emulsion synthesis of carbon-supported Pt−WO3 nanoparticles
was reported by Yang et al.997 Amorphous WO3 nanoparticles
of 1 nm in size were first deposited onto carbon from an
alkaline tungstate containing microemulsion via mixing with an
acid-containing microemulsion under microwave exposure. Pt
nanoparticles with an average size of 2.5 nm were subsequently
deposited onto the carbon-supported WO3 nanoparticles by
reducing H2PtCl6 in microemulsion by microwave heating. Jeon
et al.998 synthesized polypyrrole nanospheres (∼80 nm) using
micelles composed of tetradecyl trimethylammonium bromide
and decyl alcohol. Pt nanoparticles (∼3.2 nm) supported on
polypyrrole nanospheres were prepared using H2PtCl6·3H2O
and polypyrrole nanospheres in mixed solvents of EG, 2-
propanol, and water by a microwave-assisted process at 800 W
for 7 min, and the pH value was adjusted between 7 and 8 using
0.4 M KOH. He et al.999 synthesized La2O3/BaCO3 nano-
composites using lanthanum nitrate, barium nitrate, methyl
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oxalate, and CTAB in 1-hexyl alcohol, n-hexane, and water from
a coupling route of homogeneous precipitation with micro-
emulsion by pulsed microwave heating for 10 min. Finally, the
precursor was calcined at 800 °C for 1 h.
Zedan et al.1000 reported the microwave-assisted synthesis of
the nanocomposite consisting of CdSe nanocrystals dispersed
on graphene sheets using oleic acid, dimethyl sulfoxide, and
tributylphosphine. The reduction of graphite oxide into
graphene occurred within 2 min of microwave irradiation as
opposed to 12 h of the conventional heating at 180 °C. Cubic
and hexagonal CdSe nanocrystals with average sizes of 2−4 and
5−7 nm, respectively, were prepared by the proper choice of
the capping agent within a few minutes of microwave
irradiation. Ziegler et al.1001 reported a fast microwave-assisted
procedure for the preparation of highly luminescent CdSe
nanoparticles with ZnS shells. The effects of experimental
parameters such as the temperature, time, and shell thickness
on the luminescence quantum yield and stability of the ZnS
shell were investigated. Roy and co-workers1002 synthesized
CdSe/ZnS nanoparticles by the two-step microwave-assisted
method. In this method, CdSe cores were prepared using
Cd(CH3COO)2 and elemental Se powder in trioctyl phosphine
oxide, hexadecylamine, and trioctylphosphine. The second step
was the addition of the zinc sulfide shell using CdSe
nanoparticles as the core, and iethyl zinc (in heptane) in 1-
methyl-2-pyrrolidinone, 3-mercaptopropionic acid, hexamethyl-
disilathiane, and butylamine. Zhu et al.1003 prepared ZnO/ZnS/
γ-Fe2O3 hollow spheres using zinc acetylacetonate, ferric
acetylacetonate, and sodium bis (2-ethylhexyl) sulfosuccinate
in mixed solvents of PEG-300, oleic acid, and ethylenediamine
via microwave heating at 100 °C for 30 min. The hollow
spheres were composed of ZnO, ZnS, and γ-Fe2O3 nano-
particles, and each hollow sphere had a distinct surface hole
with the pore size of tens of nanometers or hundreds of
nanometers.
7. MICROWAVE-ASSISTED SELF-ASSEMBLY OF
NANOSTRUCTURES
Many successful examples for microwave-assisted self-assembly
of nanostructures in liquid phase have been reported, including
Pd,940 Ag,974,1004 Al,1005 Ni,528 SnO2,901 CuO,186,851 α-
Fe2O3,169,295,899 Fe3O4,522 ZnO,901 Sm2O3,951 Nd2O3,951
Gd2O3,951 NiO precursor,1006 Cd(OH)2,859 α-FeOOH,698
ZnS,962 ZnSe,962 CaCO3,868 BaCO3,391 GdF3,963 NaYF4,716,964
BiOBr,618 hydroxyapatite,350 and FeMoO4.879
Gao et al.974 prepared hexagonally arranged Ag nanoparticles
using AgNO3, dodecylthiol, EG, and toluene by one-step
microwave-assisted solvothermal interface reaction at 160−170
°C for 3 h, and a thin layer of black product formed between
the polar and the nonpolar solvents. A small amount of the
black sample was dispersed in toluene, and then a drop of this
solution was deposited on an amorphous carbon film on 300
mesh Cu grid for TEM observation directly without the
technique of size-selective precipitation. The ratio of EG/
dodecylthiol had an effect on the morphology and arrangement
of the obtained Ag nanocrystals. At a low volume ratio, Ag
nanoparticles with a rectangular shape arranged in orthogonal
arrays were observed. The TEM micrographs of the as-prepared
Ag nanocrystals are shown in Figure 28. The product consisted
of hexagonal-like ordered superstructures of monodisperse Ag
nanoparticles. The SAED pattern (Figure 28b) shows
polycrystalline diffraction rings, which can be indexed to Ag
with a cubic structure. A magnified TEM micrograph (Figure
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Figure 28. TEM micrographs, SAED pattern, Fourier transform power
spectrum, and HRTEM image of the as-prepared Ag nanocrystals.
Reprinted with permission from ref 974. Copyright 2005 American
Chemical Society.
28c) displays monodisperse spherical nanoparticles with an
average diameter of ∼10 nm and interparticle spacings of ∼2
nm. Fourier transform power spectrum (Figure 28d) shows
ordered hexagonal-like spot arrays. The HRTEM image (Figure
28e) exhibits clear lattice planes in a nanocrystal. Figure 28f
shows a TEM micrograph of two/three layers of superlattices,
the upper layer was hexagonally arranged, and these nano-
crystals were laid on the interspaces of the hexagonally arranged
nanocrystals of the lower layer.
Olgun1005 demonstrated the evaporation-induced rapid self-
assembly of 52 nm Al nanoparticles and 19 nm Ag
nanoparticles for the formation of microwires using different
surfactant−solvent formulations by microwave heating at 51−
55 °C. The formation of microwire patterns was due to stick−
slip dynamics of the contact line on the surface of the substrate.
By using microwave energy, the rapid self-assembly from metal
nanoparticles was achieved within a few minutes. Poly-
(dimethylsiloxane) was used for the purpose of promoting
microwire deposition, while Tween-20 was added as a stabilizer
for Ag nanoparticles to prevent further agglomeration and
growth in solution. The microwire deposition process
presented in this study is relatively simple as compared to
the previous patterning techniques. The use of a photoresist
layer, a micropatterned mask, a monolayer coating, and molded
patterns is not required in this method.
Cao et al.899 reported a one-step NaCl-assisted microwave-
solvothermal method for the preparation of monodisperse α-
Fe2O3 mesoporous microspheres formed by self-assembly of
nanocrystals using Fe(NO3)3·9H2O, PVP, and NaCl in mixed
solvents of water and ethanol. NaCl was found to play an
important role in the formation of monodisperse α-Fe2O3
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mesoporous microspheres. Figure 29 shows the SEM and
TEM characterization of the sample prepared at a microwave-
Figure 29. SEM and TEM characterization of monodisperse α-Fe2O3
mesoporous microspheres formed by self-assembly of nanocrystals
using Fe(NO3)3·9H2O, PVP, and NaCl in mixed solvents of water and
ethanol by the microwave-solvothermal method at 140 °C for 30 min.
(a,b) SEM micrographs; (c−e) TEM micrographs; and (f) the SAED
pattern of a single microsphere. Reprinted with permission from ref
899. Copyright 2010 Springer.
solvothermal temperature of 140 °C for 30 min. Almost
exclusive α-Fe2O3 mesoporous microspheres assembled with
nanocrystals were obtained. Figure 29f shows the SAED pattern
of a single microsphere, revealing the single-crystal-like feature
of the mesoporous microsphere formed via self-assembly of α-
Fe2O3 nanocrystals. The size of α-Fe2O3 mesoporous micro-
spheres could be controlled in the range from ∼170 to ∼260
nm by changing the experimental parameters such as the
microwave-solvothermal time and concentration of PVP. The
BET specific surface area of α-Fe2O3 mesoporous microspheres
reached as high as 114 m2 g−1. α-Fe2O3 mesoporous
microspheres obtained at a lower temperature (120 °C) had
a much higher specific surface area and narrower pore size
distribution than those of the sample prepared at a higher
temperature (140 °C). The oriented organization of smaller
nanocrystals in α-Fe2O3 mesoporous microspheres obtained at
a lower temperature (120 °C) led to a smaller average pore size
(4.3 nm); in contrast, the bigger nanocrystals in α-Fe2O3
mesoporous microspheres obtained at a higher temperature
(140 °C) resulted in a larger average pore size (7.9 nm).
Hu et al.169 adopted a microwave-assisted hydrothermal
process for the rapid synthesis of α-Fe2O3 self-assembled
hierarchically nanostructured architectures using an aqueous
solution containing K3[Fe(CN)6]. Several kinds of nanostruc-
tures, such as nanoparticles, dendritic crystals with different
sizes, plates, and self-organized nanorods, could be obtained
under different conditions. Figure 30a shows a low-magnifica-
tion TEM micrograph of a star-shaped α-Fe2O3 crystal with a 6-
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Figure 30. (a) TEM micrograph of a 6-fold-symmetric α-Fe2O3
dendrite; (b) electron diffraction pattern taken from a single dendrite,
which shows the single-crystal nature of the entire dendritic structure;
and (c and d) high-magnification TEM micrographs of the dendrite.
Reprinted with permission from ref 169. Copyright 2007 American
Chemical Society.
fold symmetry standing on the copper grid, and its
corresponding electron diffraction pattern is shown in Figure
30b. The electron diffraction patterns on different α-Fe2O3
dendrites or different positions of a given single star-shaped
crystal were essentially identical, suggesting that the α-Fe2O3
dendrite was single-crystal in nature. A close-up view of the
hierarchically nanostructured architectures revealed that the
central trunk exhibited a pagodas-like shape instead of a solid-
rod shape. Tripod-like nanocrystals of ∼100 nm as building
blocks self-assembled in a head-to-head fashion into the central
trunk. Figure 30c and d shows the high-magnification TEM
micrographs of a trunk.
Panda et al.951 prepared uniform nanorods, nanowires, and
nanoplates of rare earth oxides (M2O3, M = Pr, Nd, Sm, Eu,
Gd, Tb, Dy) using metal acetate or acetylacetonate in oleic acid
and oleylamine by the rapid microwave-assisted method with
the power set to 70% of 650 W and operated in 3 min cycles
(on for 2.5 min, off and stirring for 30 s). The reported method
allows the control of the size and shape of the rare earth oxide
nanostructures by varying the microwave reaction time and the
concentrations of the organic surfactants. The uniformity of the
nanorods and of nanowires is demonstrated in their
spontaneous assembly into highly ordered 2-D supercrystals.
To compare the effect of the microwave heating with the
conventional heating, the control experiments were performed
under reaction conditions identical to those of the microwave
experiments but using conventional thermal heating. The
resulting nanorods were significantly less uniform than those
obtained under microwave irradiation. Figure 31 shows TEM
micrographs of the self-assembly of as-synthesized Sm2O3,
Nd2O3, and Gd2O3 nanorods and nanowires. The nanorods
with an average diameter of 1.2 nm and average lengths of 4−5
nm were self-assembled into large regions of highly ordered 2-
D superstructures, as shown in Figure 31a and b. HRTEM was
used to further investigate the crystallinity and crystal structure
of the synthesized nanostructures. Distinct lattice planes in the
HRTEM image indicated that the nanostructures were single
crystals. The HRTEM image of the individual nanowire (Figure
31e) shows well-resolved lattice planes perpendicular to the
long axis with an interplanar distance corresponding to the d
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Figure 31. TEM micrographs: (a and b) Sm2O3 nanorods forming 2-
D supercrystalline assembly; (c) HRTEM of Nd2O3 nanorods, (d)
Gd2O3 nanowires; and (e) HRTEM of a Gd2O3 nanowire. Reprinted
with permission from ref 951. Copyright 2007 American Chemical
Society.
spacing of the (400) plane of the cubic Ia3 space group. The
growth mechanism for the 1-D rare earth nanostructures was
proposed.951 It was attributed to the kinetic growth, which
determined the final morphology of nanocrystals rather than
thermodynamic growth. The competitive adsorption of oleic
acid and oleylamine could inhibit the growth of the nanocrystal
in all but enhance the favorable crystallographic plane, thus
resulting in 1-D nanostructures. The crystal plane with a higher
surface energy is expected to have a faster growth rate. To
verify this mechanism, the relative concentrations of oleic acid
and oleylamine were varied. When the molar ratio of the metal
precursor/oleic acid/oleylamine was 1:17:17, spherical particles
were formed in the case of Eu2O3 nanocrystals, implying the
stronger binding capability of oleic acid relative to oleylamine.
The nanorods were formed when the molar ratio of oleylamine
to oleic acid was about 1.5 for Eu2O3 nanocrystals. However,
when oleylamine was present in much excess, square
nanoplates of Sm2O3 and Eu2O3 were formed. It was found
that the nanorods and square nanoplates were predominantly
formed when the molar ratio of metal acetate/oleic acid/
oleylamine was 1:14:22 and 1:9:27, respectively. These results
demonstrate that the control over the shape of the resulting
nanocrystals can be achieved by adjusting the capping
ligands.951
Pancake-like Cd(OH)2 superstructures were prepared via the
rapid microwave-assisted hydrothermal method at 150 °C for
10 min, adopting Cd(CH3COO)2·2H2O and hydrazine hydrate
in mixed solvents of water and glycerol. The SEM and TEM
micrographs of Cd(OH)2 multilayer stacked nanostructures are
shown in Figure 32, indicating that each architecture is
constructed by many nanoflakes via layer-by-layer self-assembly.
The SAED pattern displays ordered electron diffraction spots
and confirms the high crystallinity of the product (Figure 32d).
Several influencing factors, such as the volume ratio of
hydrazine hydrate to glycerol, reaction time, temperature, and
cadmium source, were found to play important roles in the
formation of Cd(OH)2 multilayer stacked structures. The layer-
by-layer self-assembly of nanosheets was proposed for the
formation of these superstructures.859
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Figure 32. SEM micrographs (a and b), TEM micrograph (c), and
SAED pattern (d) of Cd(OH)2 multilayer stacked structures prepared
under microwave irradiation at 150 °C for 10 min. Reprinted with
permission from ref 859. Copyright 2012 The Royal Society of
Chemistry.
The El-Shall group reported the rapid microwave-assisted
synthesis of uniform and highly aligned nanorods and
nanowires of ZnS, ZnSe, CdS, and CdSe in a mixture of
alkylamines (C6−C18) and DMF. The stepwise formation of
the nanowires from small spherical nuclei to short aligned
nanorods to long assemblies of nanowires was observed by
varying the microwave heating time from 0.5−1 min to 1−2
min to >3 min, respectively. These uniform nanorods and
nanowires spontaneously assembled into highly ordered two-
dimensional superstructures. Figure 33 displays a TEM
Figure 33. TEM micrograph of ZnS nanorods. Higher resolution
image is shown in the inset. Reprinted with permission from ref 962.
Copyright 2006 American Chemical Society.
micrograph of the as-prepared ZnS nanorods with an average
diameter of 1 nm and an average length of 5 ± 0.05 nm
synthesized with a reaction time of 2 min. The nanorods self-
assembled into arrays of highly ordered two-dimensional
superstructures.962
Wang et al.963 prepared a variety of monodisperse
GdF3:Yb,Er nanocrystals with different shapes, sizes, and
dopants by the microwave-assisted method. In addition to
monodisperse spherical nanoparticles, rhombic-shaped slices
that self-assembled into stacks were also obtained. Figure 34
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Figure 34. TEM micrographs of GdF3 rhombic nanoplates. (A)
Overview of rhombic nanoplates and “stacks”; (B) blow-up of self-
assembled rhombic nanoplates. Reprinted with permission from ref
963. Copyright 2011 Springer.
shows TEM micrographs of the as-prepared regularly shaped
GdF3 rhombic nanoplates with ∼3.2 nm in thickness and ∼45
nm in length. The nanoplates had a strong tendency to form 2-
D assemblies. Wang et al.964 synthesized monodisperse NaYF4
nanocrystals using corresponding metal trifluoroacetates in
mixed solvents of 1-octadecene and oleic acid by the
microwave-solvothermal method at 290 °C for 5 min. Figure
35A shows the TEM micrograph of NaY0.78F4:Yb3+0.2,Er3+0.02
Figure 35. (A,B) TEM micrographs of NaY0.78F4:Yb3+0.2,Er3+0.02 and
NaY 0.78F4:Yb3+0.2,Tm3+0.02 nanocrystals. (C) SAED pattern of
NaY0.78F4:Yb3+0.2,Er3+0.02 nanocrystals. (D) Fast-Fourier transform
( FFT ) image o f picture (A) . ( E) SAE D pa ttern of
NaY0.78F4:Yb3+0.2,Tm3+0.02 nanocrystals. Reprinted with permission
from ref 964. Copyright 2009 American Chemical Society.
monodisperse nanocrystals (∼11 nm). The cubic crystal lattice
was confirmed by SAED in Figure 35C. These nanocrystals self-
assembled into a regular, hexagonal 2-D arrangement over a
large area. Figure 35D shows the fast Fourier transform of
Figure 35A that confirms the hexagonal assembly of the
nanoparticles. Under the identical synthesis conditions, small
and monodisperse nanocrystals, doped with Yb3+ and Tm3+
ions, were obtained in a “cubic” morphology with a side length
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Chemical Reviews
of ∼10 nm (Figure 35B). Figure 35E (the inset of (B)) shows
that these nanocrystals had a crystalline and cubic crystal lattice.
8. COMPARISON OF MICROWAVE HEATING WITH
CONVENTIONAL HEATING
Microwave energy can significantly enhance the chemical
reaction rate, selectivity, and yield of the product. As discussed
above, the microwave-assisted synthesis can exhibit order-of-
magnitude enhancement in reaction rate as compared to the
conventional synthesis. However, the fundamental difficulties
facing all comparative studies between the microwave heating
and conventional heating, as well as between various microwave
heating studies themselves, are the accurate determination of
temperature and the inconsistencies between different experi-
ments in terms of microwave field homogeneity, reactor size
and geometry, microwave power, heating rate, heating
temperature and time, and volume of reaction systems, etc.44
The distribution of microwave energy within the reaction
mixture is also dictated by the nature and configuration of the
reactor employed. For example, the rates of nucleation and
crystallization are higher in a multimode microwave oven than
those in a single mode microwave oven with a more uniform
microwave field.2 The microwave reactor system can be
operated in various ways, such as by varying the rate at
which the temperature is increased, microwave power, stirring
of the reaction system, etc. Unfortunately, in many cases, the
comparisons have been made under different experimental
conditions such as different reaction temperatures and times.
Only a small number of researchers have taken these into
account when comparing their studies with previous microwave
syntheses and/or with conventional syntheses. In brief,
comparative studies between the microwave heating and
conventional heating should be conducted under exactly
identical experimental conditions.
It is well-known that the use of microwaves saves energy
because of fast kinetics, rapid heating, and short reaction time,
but few studies have reported the quantitative energy
consumption by microwave heating. Katsuki et al.46 inves-
tigated the approximate energy consumption calculated from
the output power. They prepared cubic BaTiO3 nanoparticles
using 8.2693 g of commercial TiO2 and 17.8935 g of Ba(OH)2
in 195 mL of distilled water at 90 °C by a home-built single-
mode semicontinuous microwave-assisted reactor. It took 1.5
min to heat the reaction system to 90 °C. Cubic BaTiO3
nanoparticles with sizes of 30−50 nm were obtained at 90 °C
for 5 min. The conversion ratio of TiO2 to BaTiO3 was 97.6%
and 100% for 5 and 15 min, respectively. However, the
conversion ratio was 62−65% at 90 °C for 15 min without
stirring, and the stirring treatment at 250 rpm was found to be a
very important factor for uniform microwave heating of the
reaction system in a large glass vessel. They found that from 22
to 90 °C, 1000 W of output (100%) was applied, and the
heating rate of the reaction system was 0.54 °C s−1. After
reaching 90 °C, the output was changed from 65 to 115 W at
90 °C for 5 min. The approximate energy consumption from
room temperature to 90 °C was 89 kJ, and 29 kJ at 90 °C for 5
min, and the total energy for the microwave-assisted synthesis
of BaTiO3 was 118 kJ. In comparison, 195 mL of distilled water
was treated at 90 °C for 5 min using the same reactor system,
the approximate energy consumption from room temperature
to 90 °C was 93 kJ, and 32 kJ at 90 °C for 5 min, respectively,
and the approximate total energy consumption was 125 kJ. To
evaluate the approximate total energy consumption by the
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conventional heating, 195 mL of water in a polyethylene vessel
was put in the oven and heated from 23 to 90 °C with the
heating rate of 5.6 °C min−1 and kept at 90 °C for 5 min. For
the conventional heating, 648 and 144 kJ were needed from 23
to 90 and 90 °C for 5 min, respectively, and total energy
consumption was 792 kJ. The conventional heating system
needed more than 6 times energy consumption of the
microwave heating system.
Horikoshi et al.111 examined the effects of the 2.45 GHz
microwave radiation on the preparation of Ag nanoparticles in
aqueous medium by reduction of [Ag(NH3)2]+ with carbox-
ymethylcellulose (CMC) in both batch-type and continuous-
flow reactor systems. The microwave-assisted preparation was
compared to the conventional heating method, both at the
same reaction temperature of 100 °C. A flow-through
microwave reactor system was used for the continuous
production of Ag nanoparticles. The flow reactor system with
a flow rate of 600 mL min−1 coupled with 1200 W microwave
radiation generated Ag nanoparticles with a size distribution of
0.7−2.8 nm (average size ∼1.5 nm). They made a comparison
of used power and heating rate between the single mode
microwave apparatus and conventional oil bath. Continuous 64
W microwave irradiation showed a rate of temperature rise of
0.51 °C s−1 for the CMC/[Ag(NH3)2]+ aqueous solution,
whereas for the oil-bath heating the rate was 0.09 °C s−1 for a
power consumption of 400 W. The much lower power of the
microwaves led to a significant enhancement of the heating rate
relative to the oil bath heating. Nishioka et al.503 reported the
continuous production of Ag nanoparticles using a homoge-
neous flow-type microwave reactor system based on a polyol
process. They also compared the performance of the flow-type
microwave heating process with that of flow-type heating by
immersion of the reactor tube in an oil bath. They prepared Ag
nanoparticle dispersions using two methods at the same
concentration of reactants, reaction temperature, and time.
For the 10 mL h−1 flow rate, the UV−vis absorption peak
intensity of the dispersion obtained by microwave heating was
almost twice that of the conventional heating, indicating the
higher yield of Ag nanoparticles by microwave heating. When
the flow rate was increased to 100 mL h−1, this effect was more
pronounced. As compared to the microwave heating, no
appreciable UV−vis absorption peak was observed for the
sample obtained by the conventional heating, suggesting that
the reaction did not occur practically by the conventional
heating at this high flow rate.
Horikoshi et al.111 reported the dielectric loss factor of the
[Ag(NH3)2]+ aqueous solution, which was 1.4-fold greater than
that of pure water, and higher than that of the CMC aqueous
system, indicating that preferential microwave heating occurred
at the [Ag(NH3)2]+ complex. By contrast, the dielectric
constants remained rather constant relative to water, whereas
the dielectric loss tangents of the initial solution and of the
[Ag(NH3)2]+/water system were otherwise identical to the Ag
colloidal solution after the 5 min microwave heating period but
somewhat greater than those of pure water and the CMC/
water solution.111 The 2.45 GHz microwaves penetrated the
aqueous medium; the microwave energy was supplied directly
and preferentially to the [Ag(NH3)2]+ complex. On the other
hand, the aqueous solution was heated by the oil bath heating
nonselectively by thermal conduction and convection through
the reactor walls to the reaction system. Thus, mechanistic
variations in microwave heating versus conventional heating are
expected to cause differences in heat interchange at the
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Figure 36. Photograph of the reactor after the reaction system was heated by two different methods: (a) microwave irradiation for 4 min; and (b) oil
bath heating for 4 min. The cartoons show the temperature distribution in the reactor: (c) after the 4 min of microwave heating; and (d) after the 4
min of oil bath heating. Experiments were carried out under nonstirring conditions. Concentrations: 0.05% w/v CMC, and 60 mM [Ag(NH3)2]+
aqueous solution. Reprinted with permission from ref 111. Copyright 2010 The Royal Society of Chemistry.

microscopic level, which leads ultimately to variations in size

distributions of Ag nanoparticles.111
The differences between the microwave heating and
conventional heating are clearly shown in Figure 36.111 The
microwave irradiation for 4 min of the [Ag(NH3)2]+/CMC
aqueous solution led to a slightly yellow-colored solution in the
reactor (Figure 36a), and Ag nanoparticles that adsorbed on the
reactor walls could be easily removed by simple washing with
water. In contrast, the Ag film (mirror) coating the inner
reactor walls formed after 4 min by the conventional heating
(Figure 36b). The initial temperature distributions and
formation of Ag nanoparticles under nonstirring conditions
by both the microwave and the conventional heating are shown
in the cartoons of Figure 36c and d.111 In the former case,
microwave radiation penetrated the [Ag(NH3)2]+/CMC
aqueous solution causing the temperature to rise by dielectric
loss and to some extent by conduction heating, followed by
subsequent loss of heat to the surroundings through the reactor
walls. As a result, the temperature near the inner walls of the
reactor tended to be lower than that at the center of the reactor.
That is, the preparation of Ag nanoparticles by the microwave- Figure 37. TEM micrographs and particle size distributions of Ag
assisted process progressed outward from the center of the nanoparticles produced under microwave irradiation (a and c) and oil
reactor to the inner reactor walls due to a temperature gradient bath heating (b and d). Concentrations: 0.05% w/v CMC, and 60 mM
that gave rise to a concentration gradient. In contrast, heat from [Ag(NH3)2]+ aqueous solution. Reprinted with permission from ref
the oil bath was most prominent at the reactor walls and was 111. Copyright 2010 The Royal Society of Chemistry.
subsequently transmitted to the solution by the thermal
conduction and convection mechanism, leading to the though the reaction temperature conditions for the microwave
formation of a Ag film at the reactor inner walls due to higher heating and oil bath were identical, there was a noticeable
concentration of the nanoparticles. Schanche28 and Kappe29 difference in the formation rate of Ag nanoparticles and their
discussed temperature distributions produced by microwave size distributions.
and conventional heating methods in organic syntheses. Katsuki et al.164 prepared monodisperse α-Fe2O3 nano-
Horikoshi et al.111 investigated the effect of the heating particles using Fe(NO3)3·9H2O solutions by the microwave-
methods on the formation of Ag nanoparticles in aqueous hydrothermal and conventional-hydrothermal reactions. As
solution by reduction of [Ag(NH3)2]+ with CMC. Figure 37a compared to the conventional-hydrothermal reaction, the
and b shows the TEM micrographs of the resulting Ag microwave-hydrothermal reaction led to increased formation
nanoparticles. A fairly monodispersed particle size distribution rate by 3 times at 120 °C and 5 times at 140 °C from 0.1 M
was observed by microwave heating (1.8−3.6 nm, average size Fe(NO3)3·9H2O solutions. Kijima et al.1007 synthesized α-
∼3 nm) under temperature conditions otherwise identical to Fe2O3 nanoparticles with an average diameter of less than 10
those of the conventional heating, which produced a broader nm using Fe(NO3)3·9H2O as the only starting reagent in
size distribution (1−5 nm). By contrast, light scattering aqueous solution by continuous microwave heating for 2 min in
measurements indicated a size distribution by microwave a modified household microwave oven. Figure 38 shows the
heating in the range of 1−2.3 nm (Figure 37c), whereas the photographs of the reaction solutions that were microwave-
conventional heating led to polydipsersed nanoparticles mostly heated and conventionally heated. When the solution was
in the range of 3−5.7 nm (Figure 37d) with some nanoparticles irradiated with microwaves continuously, the temperature of
up to 30 nm. These experimental results indicate that even the solution was increased rapidly to 100 °C within 80 s, and
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Chemical Reviews Review

Figure 38. Time course of the color of the reaction solutions that were microwave-heated and conventionally heated. Reprinted with permission
from ref 1007. Copyright 2010 Elsevier B.V.

the color of the solution changed from bright yellow to wine

red, indicating that a colloidal dispersion formed. Although no
stabilizer existed in the solution, the colloidal dispersion was
stable. In contrast, when the solution was heated by a magnetic
hot-stirrer, the temperature of the solution was increased
gradually. After 30 min, a reddish-brown suspension was
obtained. The XRD pattern confirmed that α-Fe2O3 rapidly
formed by microwave heating. Even if the microwave heating
was 1 h, α-FeOOH was not observed in the product. In
contrast, a mixture of α-Fe2O3 and α-FeOOH was obtained by
the conventional heating for 1 h.
Katsuki et al.269 prepared BaTiO3 nanoparticles using
commercial TiO2 and Ba(OH)2 in distilled water by the
microwave heating and conventional heating at 90 °C. As
compared to the formation of BaTiO3 nanoparticles using the
conventional heating process, the microwave-assisted process
led to increased formation rate by about 6 times. For a reaction
time of 1 min, the conversion ratio of TiO2 to cubic BaTiO3
powder was 73.7% and 0% by microwave heating and
conventional heating, respectively. For a reaction time of 5
min, the conversion ratio of TiO2 to cubic BaTiO3 reached
95.8% by microwave heating; however, the conventional
Figure 39. (a) TEM micrograph and (b) the histogram of Ag particle
heating still led to 0% conversion ratio. The conversion of
size distribution of the PAM/Ag nanocomposite prepared by
TiO2 to BaTiO3 reached 100% after only 10 min via microwave microwave heating an EG solution of 0.01 M AgNO3 and 3 M
irradiation but after 1 h via the conventional process. BaTiO3 acrylamide at 125 °C for 15 min. (c) TEM micrograph and (d) the
nanoparticles with an average size of 29 nm were obtained after particle size distribution of the PAM/Ag nanocomposite prepared by
treatment for 15 min by microwave heating. The experiments oil bath heating an EG solution of 0.01 M AgNO3 and 3 M acrylamide
showed that the use of microwaves led to the formation of at 125 °C for 150 min. Reprinted with permission from ref 470.
smaller nanoparticles with a narrower size distribution as Copyright 2006 American Chemical Society.
compared to that of the conventional heating process.
Zhu et al.470 prepared the nanocomposites of polyacrylamide 10−26 nm (Figure 39c,d), which were larger than those
(PAM)/metal (Pt, Ag, Cu) with metal nanoparticles homoge- prepared by microwave heating at the same temperature with
neously dispersed in the polymer matrix using the correspond- the same reaction solution. The PAM/Ag nanocomposite with
ing metal salt and acrylamide monomer in EG by the rapid a larger average Ag particle size and a broader particle size
microwave-assisted polyol method. The diameters of Ag distribution was obtained by microwave heating at a higher
nanoparticles in the PAM/Ag nanocomposite were in the temperature for 15 min or at 125 °C for a longer reaction time.
range of 6−18 nm with an average diameter of 11.3 nm Katsuki and Komarneni1008 prepared monodisperse α-Fe2O3
prepared by microwave heating the EG solution of 0.01 M nanoparticles using 0.018 M FeCl3·6H2O and 0.01 M HCl
AgNO3 and 3 M acrylamide at 125 °C for 15 min, as shown in solutions in the temperature range of 100−160 °C via the
Figure 39a,b. For comparison, the synthesis of the PAM/Ag microwave-hydrothermal (M-H) and conventional-hydrother-
nanocomposite was also conducted by the conventional oil bath mal (C-H) method. Acicular β-FeOOH structures with 300 nm
at 125 °C; however, much longer reaction time (about 2.5 h) in length and 40 nm in thickness were dominantly formed at
was needed to obtain the PAM/Ag nanocomposite with an 100 °C for 2−3 h, while spherical α-Fe2O3 particles with 100−
average Ag diameter of 16.9 nm and a wide size distribution of 180 nm in diameter were preferentially formed for 13 h using
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Figure 40. Effect of microwave heating on the kinetics of hydrothermal formation of α-Fe2O3 nanoparticles at 100, 120, and 140 °C. Reprinted with
permission from ref 1008. Copyright 2001 American Ceramic Society.

Figure 41. Yields of LaF3:Ce,Tb nanoparticles (a) and LaPO4:Ce,Tb nanorods (b) at different reaction temperatures using different heating sources.
The inset images show the appearance of samples obtained from microwave heating and oil bath under a 254 nm ultraviolet lamp and natural light.
Reprinted with permission from ref 616. Copyright 2010 The Royal Society of Chemistry.

the conventional-hydrothermal method. In contrast, the
microwave-hydrothermal reaction at 100 °C led to mono-
disperse α-Fe2O3 nanoparticles with 30−66 nm in diameter
after 2 h without the formation of β-FeOOH. Figure 40 shows
the yields of α-Fe2O3 at 100−140 °C for different reaction
times via the C-H and M-H reactions. From Figure 40, one can
see that the ratios of the kinetics K = VM‑H/VC‑H were 1.6 and
2.5 at 100 and 120 °C, respectively, but increased to ∼5 at 140
°C. The yields of α-Fe2O3 particles obtained by the M-H
reaction reached 83%−95% at 140−160 °C after 2−4 h.
Zhu et al.616 reported the rapid synthesis of LaF3:Ce,Tb and
LaPO4:Ce,Tb nanocrystals using EG as the solvent by adopting
a microwave-heated microfluidic reactor. They performed
comparative experiments between the microwave heating and
oil bath. The sizes of LaF3:Ce,Tb nanoparticles obtained by
microwave heating were obviously smaller and more uniform
than those prepared by oil bath. Figure 41 shows the product
yields at different temperatures from different heating sources.
It was found that the yields of the microwave-prepared samples
were higher than those of the oil bath prepared samples at each
temperature with the highest yield of 72.3% for LaF3:Ce,Tb
nanoparticles and 91.2% for LaPO4:Ce,Tb nanorods. The inset
images in Figure 41 indicate the differences in the yield %
visualized between samples.
Dahal et al.1009 investigated the effects of the microwave
heating versus conventional heating on the nucleation and
growth of nearly monodisperse Rh, Pd, and Pt nanoparticles.
They adopted a one-pot synthetic method, which combined the
6532
nucleation and growth in a single reaction system via precise
control over the precursor addition rate. The microwave
heating enabled the convenient preparation of polymer-capped
metal nanoparticles with improved monodispersity, morpho-
logical control, and higher crystallinity, as compared to samples
obtained by the conventional heating under otherwise identical
conditions. The fundamental difference in Rh nanoparticle
formation was observed during the nucleation stage that was
directly dependent on the heating method. The microwave
heating led to faster nucleation and also the formation of more
uniform nanoparticles as compared to the oil bath. Microwave
irradiation was found to provide more uniform seeds for the
subsequent crystal growth. Nanoparticle growth kinetics by
microwave heating was also different as compared to the
conventional heating. The conventional heating generally
produced nanostructures with mixed morphologies, while
microwave synthesis produced a majority of tetrahedral
nanocrystals with sizes of 5−7 nm or larger nanocubes (>8
nm) upon further growth. Rh seeds and larger nanoparticles
obtained from microwave-assisted synthesis were more highly
crystalline and faceted as compared to their conventionally
prepared counterparts.
The overall comparative trends in size of Rh nanostructures
prepared by both microwave heating and conventional heating
are shown in Figure 42.1009 The control over particle size as a
function of total added RhCl3 precursor was achieved under
both modes of heating. The smaller conventionally prepared
seeds (Figure 42A, blue data) resulted in accordingly smaller
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Chemical Reviews
Figure 42. (A) Average sizes of initial Rh seeds (open symbols) and
after ripening (solid symbols) as a function of precursor injection rate.
(B) Size and standard deviation of Rh nanoparticles as a function of
the amount of added RhCl3 precursor. Blue stands for conventional
heating; red stands for microwave heating. Reprinted with permission
from ref 1009. Copyright 2012 American Chemical Society.
Rh nanoparticles (Figure 42B, blue data) as compared to those
of larger microwave-derived seeds (Figure 42A, red data).
Microwave-prepared Rh nanoparticles exhibited approximately
twice the catalytic activity of similarly sized conventionally
prepared nanoparticles in the vapor-phase hydrogenation of
cyclohexene. The microwave heating resulted in the complete
exchange of PVP capping agent with oleylamine and oleic acid.
In contrast, similar ligand exchange was difficult by the
conventional heating.
To understand quantitatively which stage of the nucleation
or crystal growth is selectively accelerated under microwave
irradiation, Jhung et al.30 synthesized silicalite-1 and VSB-5
molecular sieves by the conventional electric heating (CE) and
microwave heating (MW). They considered three cases of
acceleration in the microwave synthesis: (1) acceleration both
in nucleation and in crystal growth, (2) acceleration in
nucleation only, and (3) acceleration in crystal growth only.
The syntheses were performed in two steps, that is, MW−MW,
MW−CE, CE−MW, and CE−CE (in the order of nucleation−
crystal growth). They found that microwave irradiation
accelerated not only nucleation but also crystal growth as
compared to the conventional heating. However, the effect of
microwave irradiation appeared to be much more significant on
the nucleation relative to crystal growth (Figure 43). The
reaction rates of the nucleation and crystal growth were
analyzed by using crystallization curves of silicalite-1 and VSB-
5. As shown in Figure 43, the syntheses of silicalite-1 had
different induction periods (crystallization time needed to show
any crystallinity), different synthesis times to complete the
crystallization, and the slopes of crystallinity changed depend-
ing on the reaction modes.
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Figure 43. Change of crystallinity of a microporous material with time
to show several modes of accelerations: (a) both nucleation and
crystallization are accelerated; (b) only nucleation is accelerated; (c)
only crystallization is accelerated; and (d) normal synthesis without
any acceleration. Reprinted with permission from ref 30. Copyright
2007 Wiley-VCH.
Figure 44 shows the crystallization curves of silicalite-1
prepared under microwave irradiation and/or conventional
Figure 44. Crystallization curves of silicalite-1 prepared under
microwave irradiation (MW) and/or conventional electric heating
(CE), showing crystallinity changes depending on the synthesis
method and reaction time. Reprinted with permission from ref 30.
Copyright 2007 Wiley-VCH.
electric heating, showing crystallinity changes according to the
synthesis method and reaction time. The overall synthesis time
for the completion of crystallization under microwave
irradiation was around 3 h, whereas ∼90 h was needed to
complete the crystallization with the conventional heating
(Figure 44a and d). Therefore, the cumulative degree of
acceleration by microwaves was around 30-fold. The slope of
the crystallization curve obtained by microwave heating was
more steep as compared to that by the conventional heating,
indicating that the crystallization stage is accelerated by
microwave heating. Irrespective of the first heating method,
crystallization under microwave irradiation was quite rapid.
However, the crystal growth by the conventional heating
depended mainly on the initial heating method. The crystal
growth by the conventional heating was quite fast for the
sample nucleated by microwave irradiation relative to the very
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Chemical Reviews
Figure 45. (a) Time-dependent evolution of the crystal size (green curve), yield of ZnO powder (black curve), and zinc acetate concentration (red
curve) by microwave heating at 120 °C. (b) TEM overview micrograph of ZnO nanoparticles obtained by microwave heating at 120 °C for 3 min
(inset: HRTEM image of one nanoparticle). Reprinted with permission from ref 772. Copyright 2009 American Chemical Society.
slow crystallization of the sample nucleated by the conventional
heating. The times needed for crystallization were about 2 and
4−80 h with microwave irradiation and conventional heating,
respectively. The nucleation time of silicalite-1 was also reduced
from 10 to 1 h by microwave heating, indicating the high
efficiency of microwave irradiation in the acceleration of
nucleation. Because of the acceleration in both stages, the
overall synthesis times for silicalite-1 and VSB-5 decreased by
about 30- and 12-fold, respectively, by using microwave heating.
The crystal sizes of silicalite-1 and VSB-5 increased in the order
of the products synthesized by MW−MW > MW−CE > CE−
MW > CE−CE. The rapid crystal growth and small crystal size
observed in the synthesis from the microwave-nucleated
precursor can be explained in terms of the fact that the
microwave-nucleated samples have higher population of nuclei
with smaller sizes than the samples nucleated by the
conventional heating.
Campelo et al.922 compared the microwave synthesized metal
(Au, Ag, or Pd) nanoparticles supported on mesoporous
material SBA-12 with those obtained under the conventional
heating under the same conditions (temperature and heating
time). They found that the conventional heating preparation
led to an extremely low metal loading with a poor dispersion of
supported metal nanoparticles, and higher nanoparticle loading
was only achieved at relatively long heating times (over 1 h),
and uneven distribution and dispersion of metal nanoparticles
were also observed. The rapid heating of the reaction mixtures,
especially those containing polar solvents (e.g., ethanol and
water), by microwaves led to a rapid and almost simultaneous
formation of metal nanoparticles with small particle sizes and
narrow size distributions at very short reaction times (less than
3 min). Bhattacharya et al.1010 reported the preparation of
aqueous ferrofluids by chemical coprecipitation of iron salts in
poly(vinyl alcohol) by both conventional and microwave
heating modes. They found that for the same initial
constituents, microwave irradiation enhanced the saturation
magnetization of the product more than double as compared to
that prepared by the conventional heating. Microwave
irradiation increased the polydispersity, average particle size,
and crystallinity of the product.
Bilecka et al.772 reported a detailed investigation of the
kinetics and thermodynamics in the microwave-assisted syn-
thesis of ZnO nanoparticles from Zn(CH3COO)2 and benzyl
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Review
alcohol at temperatures ranging from 120 to 180 °C for 0.5−35
min. They also investigated the organic esterification reaction
between acetate and benzyl alcohol, and the formation and
growth of ZnO nanoparticles. Monitoring both the formation
of the organic species as well as the crystal size of ZnO with
time directly correlated the kinetics of the organic side reaction
with the growth kinetics of ZnO nanoparticles. The
esterification reaction, which is the chemical basis for producing
the monomer for ZnO formation, was found to be first order.
The growth of ZnO nanoparticles followed the Lifshitz−
Slyozov−Wagner model for coarsening, indicating a diffusion-
limited process. For comparison, the synthesis of ZnO was also
carried out at 120 °C in an oil bath under otherwise identical
reaction conditions. As compared to the conventional heating,
the microwave irradiation greatly accelerated nanoparticle
formation by (a) facilitating the dissolution of the precursor
in the solvent, (b) increasing the rate constant for the
esterification reaction by 1 order of magnitude, resulting in
faster production of monomer and consequently in an earlier
nucleation event, and (c) increasing the rate constant kgrowth for
the crystal growth from 3.9 nm3 min−1 for the conventional
heating to 15.4 nm3 min−1 for the microwave heating.772
Figure 45a illustrates the relation between the yield of ZnO
powder (black curve), crystal size (green curve), and
Zn(CH3COO)2 concentration (red curve) at 120 °C for
different microwave heating times.772 It took about 5 min of
microwave heating at 120 °C to obtain phase-pure ZnO
nanoparticles, and the crystal size grew continuously with
increasing microwave heating time (Figure 45a, green curve),
and Zn(CH3COO)2 was gradually consumed due to the
esterification reaction (Figure 45a, red curve). The concen-
tration of Zn(CH3COO)2 decreased from the initial concen-
tration C0 (C0 = 100%) to about 35−40% within 18 min, then it
little changed (Figure 45a, red curve). The yield of ZnO
increased with time, but reached a maximum value of about
80% after ∼18 min and then remained almost constant.
Comparison of the ZnO yield with Zn(CH3COO)2 concen-
tration showed an inversely related behavior with comparable
kinetics. With decreasing Zn(CH3COO)2 concentration, the
ZnO yield increased, and both values became almost constant
after 18 min; that is, the system reached a dynamic equilibrium
between the dissolved monomer and the solid ZnO. However,
the crystal size of ZnO still increased with microwave heating
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Chemical Reviews
Figure 46. Comparison of benzyl acetate (a,c) and ZnO formation (b,d) by microwave heating (red) and conventional heating (black) at 120 °C.
(a) Zinc acetate concentration versus reaction time, (c) corresponding first-order kinetic plot. (b) Radius of ZnO nanocrystals versus reaction time,
(d) r3 versus time according to the Lifshitz−Slyozov−Wagner (LSW) model. Reprinted with permission from ref 772. Copyright 2009 American
Chemical Society.
time, indicating that the Ostwald ripening was the only growth
mode for longer reaction times. Figure 45b shows a TEM
micrograph of ZnO nanoparticles with diameters from 10 to 25
nm obtained by microwave heating at 120 °C for 3 min, and a
HRTEM image of a single ZnO nanoparticle exhibiting the
single-crystalline nature in structure. Bilecka et al.772 proposed
that the acceleration effect of microwave irradiation is mainly
based on kinetic rather than thermodynamic factors, because no
experimental indication was found that the activation energy for
ester formation or for crystal growth was significantly lowered.
It was reported that the activation energy was determined to be
37 kJ mol−1 for the benzyl acetate formation, and 60 kJ mol−1
for ZnO crystal growth.772
For comparison, Bilecka et al.772 also performed experiments
by the conventional heating in an oil bath preheated at 120 °C
under otherwise similar conditions, and the obtained
experimental results are summarized in Figure 46. The faster
dissolution rate of the precursor contributed to the shorter
precipitation time of ZnO under microwave irradiation in
comparison to the conventional heating. However, microwave
irradiation also affected the organic esterification reaction. The
change of zinc acetate concentration at 120 °C versus time
shows a significant difference between microwave heating (red
curve) and conventional heating (black curve) (Figure 46a),
which consequently led to different rate constants (Figure 46c).
For the conventional heating, the rate constant kesterification was
0.0142 min−1; however, the rate constant was 0.124 min−1 for
the microwave heating, which corresponds to a kinetic
enhancement of almost 1 order of magnitude. Faster
esterification also means faster increase in the monomer
concentration, suggesting that the nucleation occurs earlier for
the microwave-assisted synthesis. In addition to the ester-
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ification reaction, the crystal growth of ZnO was greatly
enhanced by microwave heating (Figure 46b). The correspond-
ing rate constant kgrowth, obtained from the LSW analysis, was
15.36 nm3 min−1 for the microwave heating and only 3.9 nm3
min−1 for the conventional heating (Figure 46d), which means
that the crystal growth rate under microwave irradiation was
about 4 times that by the conventional heating. These
experimental results are consistent with the work by Jhung et
al.30 on the microwave-assisted synthesis of microporous
materials, which has also shown that microwave irradiation
accelerated both the nucleation and the crystal growth with a
more obvious effect on the nucleation stage relative to crystal
growth.
There have been some conflicting reports on the activation
energies for chemical reactions under microwave irradiation,
and more careful investigations are needed to clarify this issue
in the future. Some papers have reported that the activation
energies for microwave-assisted processes are smaller than
those by the conventional heating. For example, Lewis et al.1011
discussed a mechanism based on temperature difference for the
microwave-enhanced reaction of imidization in solution. The
apparent activation energy for the reaction was reduced from
105 to 55 kJ mol−1 when microwave radiation was utilized
under the experimental conditions they employed. They
proposed a mechanism to explain this enhancement based on
the concept of a nonuniform temperature on a molecular scale,
rather than a true reduction in the activation energy. They
proposed that the pulsed microwave energy would produce
effects different from those produced by the continuous
microwave irradiation. Brosnan et al.1012 investigated the
sintering kinetics and microstructural evolution of alumina
tubes by the conventional heating and microwave heating at
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Chemical Reviews
Table 2. Calculated Pre-exponential Factors (A) and Activation Energies (Ea) in the Arrhenius Equation k = A e−Ea/RT and
Activation Free Energy (ΔG) for the Nucleation and Crystal Growth in the Synthesis of Cu2O Crystals by Three Different
Methodsa
A for nucleation Ea for nucleation ΔG for nucleation
synthesis method (min−1) (kJ mol−1) (kJ mol−1)
ultrasound 2.72 × 1011 72.7 91.3
irradiation
microwave 1.36 × 10 9
61.5 94.7
heating
conventional 9.23 × 104 44.1 103
heating
a
The data were collected from ref 1014.
Figure 47. Crystallization curves for the synthesis of Cu2O crystals by three different methods: (a) microwave heating; (b) conventional heating.
Reprinted with permission from ref 1014. Copyright 2011 The Royal Society of Chemistry.
2.45 GHz. With no hold time at the sintering temperature,
microwave-sintered samples reached 95% density at 1350 °C
versus 1600 °C for conventionally heated samples. The
activation energy for microwave sintering was 85 ± 10 kJ
mol−1; in comparison, the activation energy for the conven-
tional sintering was 520 ± 14 kJ mol−1. Fang et al.1013
investigated the kinetic mechanism of the microwave cure of
3,4′-bis[(4-phenylethynyl)phthalimido]diphenyl ether (PEPA-
3,4′-ODA) and phenylethynyl-terminated imide oligomer
(PETI-5). The microwave cure of PEPA-3,4′-ODA and
PETI-5 was investigated using a variable frequency microwave
furnace. As compared to the conventional thermal curing rate
studies of these two materials, the microwave cure gave much
higher rate constants for both. The activation energy of the
microwave cure was 68% that of the thermal cure for PEPA-
3,4′-ODA, and 51% that of the thermal cure for PETI-5.
However, in some reports, the activation energies for
microwave-assisted processes were even higher than those by
the conventional heating. For example, Haque et al.1014
reported that the activation energies for the nucleation and
crystal growth in the microwave-assisted synthesis of Cu2O
crystals were higher than those by the conventional heating
(Table 2). The calculated activation energy for the nucleation
of Cu2O was 61.5 kJ mol−1 by the microwave heating and 44.1
kJ mol−1 by the conventional heating. In contrast, the activation
energy for the crystal growth of Cu2O crystals was 75.1 kJ
mol−1 by the microwave heating and 58.6 kJ mol−1 by the
conventional heating. It was also reported that the activation
energies for the microwave-assisted synthesis of porous
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A for crystal growth Ea for crystal growth ΔG for crystal growth
(min−1) (kJ mol−1) (kJ mol−1)
5.32 × 1012 84.7 94.4
2.92 × 10 10
75.1 99.0
2.81 × 106 58.6 107
materials such as metal−organic frameworks and aluminophos-
phates were higher than those by the conventional heating.1015
Haque et al.1014 compared the effects of the heating methods
on the acceleration and yield of Cu2O crystals. Three different
methods including the conventional heating (CE), ultrasound
irradiation (US), and microwave heating (MW) were adopted
using an aqueous solution containing CuSO4·5H2O, Na2CO3,
sodium citrate, and PVP. The reaction was carried out at a low
temperature (up to 50 °C) to take advantage of low reaction
rates for a precise comparison. Cu2O crystals with a cubic
morphology were obtained by ultrasound irradiation and
microwave heating; however, a mixture of multipod and
truncated octahedra was formed by the conventional heating.
Cu2O crystals obtained by the conventional heating had various
sizes and shapes due to concomitant nucleation and crystal
growth and long reaction time. The accelerated synthesis with
microwaves or ultrasound was explained with the activation
energy, pre-exponential factor, and thermodynamic parameters.
The rapid microwave-assisted synthesis (acceleration degree
was 17−18 times of the conventional heating) was explained by
a significant increase in the pre-exponential factor of the
Arrhenius equation or decreased activation free energy (ΔG) of
the Eyring equation even though the activation energies (Ea)
were increased under microwave irradiation. The decreased ΔG
was due to the small decrease (or relatively high) in activation
entropy (ΔS) rather than low activation enthalpy (ΔH). The
activation energy decreased in the order of ultrasound synthesis
> microwave synthesis > conventional heating synthesis. They
proposed that the acceleration by microwave heating is mainly
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Chemical Reviews
due to physical effects including hot spots or transient
temperature rather than chemical ones.
It was found that the crystallinity of Cu2O prepared by
microwave heating was dependent on the reaction temperature
and time.1014 As shown in Figure 47, the crystallinity of the
product changed with the reaction temperature, time, and
synthetic methods. The crystallinities of Cu2O obtained with
different methods are compared in Figure 48 at the same
Figure 48. Crystallization curves of Cu2O crystals synthesized at 40 °C
by three different methods. Reprinted with permission from ref 1014.
Copyright 2011 The Royal Society of Chemistry.
reaction temperature of 40 °C. All of the crystallization curves
exhibited the typical sigmoid form, which has been widely
observed in the syntheses of solid materials. As shown in Figure
47, the fully crystallized Cu2O was obtained in around 30−90,
60−120, and 1000−3000 min with ultrasound (30−40 °C),
microwaves (40−50 °C), and conventional heating (40−50
°C), respectively, showing the synthesis rates were in the order
of ultrasound > microwave ≫ conventional heating. The rates
for nucleation and crystal growth were evaluated with the time
of first appearance of XRD peaks and the slope of crystallization
curves of Figure 47, respectively. The crystallization rate was
very rapid for the synthesis by both ultrasound irradiation and
microwave heating. In contrast, the crystallization rate was very
slow for the synthesis by the conventional heating. The
crystallization curves of Cu2O crystals at the same temperature
Figure 49. Yields (a) and particle sizes (b) of Cu2O crystals versus reaction time prepared at 40 °C by three different methods. Reprinted with
permission from ref 1014. Copyright 2011 The Royal Society of Chemistry.
6537
Review
of 40 °C (Figure 48) also indicate the relative crystallization
rates of three methods (ultrasound > microwave ≫ conven-
tional heating).
Haque et al.1014 compared the product yields by using
different methods at the same reaction temperature of 40 °C, as
shown in Figure 49a. The yield of the product increased with
increasing reaction time or increasing reaction temperature, and
the yield changed in the order of ultrasound > microwave >
conventional heating. Figure 49b shows that the average
particle size of Cu2O crystals increased with increasing reaction
time.
Haque et al.1015 reported the synthesis of porous materials
such as metal−organic frameworks and aluminophosphates by
microwave heating and conventional heating at various
temperatures for different times to investigate the quantitative
acceleration in the microwave-assisted synthesis of porous
materials. The acceleration degrees (rMW/rCE) for nucleation
and crystal growth by microwave heating were 4.9−32.7 and
20.5−35.9, respectively. There was little effect of the types of
porous materials and types of metal ions (Al3+, Cr3+, and V4+)
in isotypic metal−organic frameworks on the acceleration
degrees in the microwave syntheses of porous materials. Their
studies indicated that the free energy (ΔG) of microwave
synthesis was lower than that of the conventional synthesis.
However, the activation enthalpy (ΔH) and activation entropy
(ΔS) were higher for the microwave-assisted synthesis. They
proposed that the acceleration by microwaves was mainly due
to decreased activation free energy even though the activation
energy and activation enthalpy increased. The decreased
activation free energy of the microwave synthesis was mainly
due to the higher activation entropy of microwave synthesis as
compared to that of the conventional synthesis. They proposed
that accelerated synthesis with microwaves may be due to
changes of relative energies of the intermediates. The relative
thermodynamic parameters of microwave and conventional
syntheses are summarized in Figure 50. Even though the
detailed reasons of the difference in thermodynamic parameters
could not be clearly explained, they explained the microwave-
accelerated synthesis with a more favorable reaction coordinate
(selective heating and changing the reaction profile) or changes
of relative energies of the intermediates for high activation
entropy with increased randomness.
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Chemical Reviews Review

the preparation of inorganic nanostructures in liquid phase,

Figure 50. Suggested relative activation free energy, enthalpy, and
entropy changes with synthesis methods (CE = conventional heating;
MW = microwave heating). Reprinted with permission from ref 1015.
Copyright 2011 The American Chemical Society.
Although obvious differences between the microwave heating
and conventional heating have been reported in many cases for
there have been some reports in which no obvious differences
between the microwave heating and conventional heating could
be observed. For example, Gutmann et al.1016 investigated the
electromagnetic field effects on 21 selected chemical reactions
by comparing the results obtained in microwave-transparent
Pyrex vials with the experiments performed in SiC vials at the
same reaction temperature. For most of the 21 reactions, the
results in terms of the conversion, purity, and product yield
using the two different types of vials were virtually identical,
indicating that the electromagnetic field had no direct influence
on the reaction pathway. Obermayer et al.54 used a reaction
vessel made out of SiC, in combination with a single-mode
microwave reactor that allows simultaneous temperature
monitoring by external infrared and internal fiber-optic probes.
Their experimental setup provided a means to heat a reaction
system by a conventional heat transfer mechanism and not by
dielectric heating effects, although using microwave irradiation.
Eighteen previously reported microwave-assisted organic
chemical reactions were investigated in comparison with the
conventional heating; however, they did not find any significant
differences in terms of the conversion, purity, and product yield
between experiments performed in microwave-transparent
Pyrex and SiC vials.
Pein et al.809 investigated the synthesis of CuInS2 nano-
particles using CuI, InCl3, and elemental S in oleylamine as a
solvent and capping agent. They carefully carried out the
comparative experiments by microwave heating using Pyrex and

Figure 51. Comparison of CuInS2 nanoparticles synthesized at 220 °C by different heating methods: (A) TEM micrograph and SAED pattern
(inset) of the sample obtained by microwave-Pyrex; (B) TEM micrograph and SAED pattern (inset) of the sample obtained by microwave-SiC; (C)
TEM micrograph and SAED pattern (inset) of the sample obtained by oil bath; (D) heating profiles of the comparative experiments; and (E) XRD
patterns of the samples obtained after 15 min overall reaction time. Reprinted with permission from ref 809. Copyright 2010 The American
Chemical Society.

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Chemical Reviews
SiC vials and conventional heating using SiC vials under
otherwise identical reaction conditions. In all cases, the desired
final temperature was 220 °C, and the overall heating period
(including ramp and hold time) was 15 min. The experiments
showed that the samples had the same crystal phase with
similar primary crystallite sizes of ∼5.4 nm. The TEM
micrographs in Figure 51 indicate similar nanoparticle shapes
and size distributions in the range between 5 and 10 nm. Both
TEM and XRD experiments could not identify significant
differences between two heating modes. The only small
difference observed was that the microwave-prepared sample
had a somewhat higher amount of capping ligand, detected by
the thermogravimetric analysis. Carefully executed control
experiments, ensuring identical heating and cooling profiles,
stirring rates, volumes and concentrations of reactants, and
reactor geometries, demonstrated that for the preparation of
CuInS2 nanoparticles no differences between the microwave
irradiation and conventional heating could be observed.809
9. FUTURE PROSPECTS AND CHALLENGES
In summary, as demonstrated in a large number of publications
in the literature, the remarkable advantages of the microwave
heating technology are rapid volumetric heating, higher
chemical reaction rate and selectivity, shorter reaction time,
and higher product yield as compared to the conventional
heating methods. In many cases, the microwave-assisted
syntheses exhibit order-of-magnitude enhancements in chem-
ical reaction rate as compared to the conventional syntheses. As
a result, the microwave heating as a novel heat source allows
the rapid production of inorganic nanostructured materials in
liquid phase, leading to relatively low cost, energy savings, and
high efficiency, thus advancing rapidly toward its practical
applications. On the other hand, the rich varieties of liquid
solvents and their smart combinations will provide a great
freedom for the rapid preparation of various nanostructured
materials, and more importantly for the control over the
chemical composition, structure, size, morphology, and self-
assembly, thus greatly expanding the applications of the
microwave heating technology in materials science. Therefore,
the microwave heating technology has been emerging as an
alternative heat source for rapid chemical reactions and
materials preparation in minutes, instead of hours or even
days usually required by the conventional heating methods.
Consequently, the microwave heating technology has been
receiving an exponential increase in acceptance, as evidenced by
a rapidly increasing number of publications each year. It is
expected that the use of the microwave heating technology as
an alternative heat source will become more popular in many
research laboratories and even in industry. The microwave-
assisted rapid preparation of inorganic nanostructures in liquid
phase is currently a fast-growing area of research, and the
research activities will continue to rapidly expand in the coming
years. Although the overwhelming number of microwave-
assisted applications are still performed on a laboratory
(milliliter) scale, it is expected that this novel technology will
be able to scale up for the industrial production in the near
future.
However, some challenges still exist and need to be
overcome. For example, one major problem is that many
published papers did not provide detailed experimental
parameters, which are essential for the repeat by other
researchers, and the information on the microwave reactors
employed and the reaction containers was rarely documented.
6539
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In some cases, the types of the microwave ovens, typically
domestic microwave ovens, were even not mentioned. Many
early reports on the microwave-assisted syntheses were carried
out in household microwave ovens, and the reproducibility
varied with the brand of the instrument, and the size and
geometry of the microwave cavity. The microwave heating
temperatures were not accurately measured and even not
reported in many early published papers. Thus, these reported
experiments are difficult to be repeated and compared by other
researchers. Therefore, the use of specially designed microwave
reactors with the ability to accurately measure and control the
temperature is strongly recommended. With the development
of the microwave instrumentation technology, together with
the reasonable cost and simplicity of its use, researchers now
have easy access to commercial microwave reactors with
temperature and pressure monitoring by various probes and
sensors, built-in magnetic stirring, power control, cooling
system, and software operation. It is expected that more
microwave-assisted syntheses will be performed using micro-
wave ovens specifically designed for chemical reactions and
materials synthesis, which allow precise control of the various
experimental parameters and good repeatability. On the other
hand, it is strongly suggested that the experimental description
in publications for the microwave-assisted synthesis should be
as specific and detailed as possible.
Because the mechanisms of the microwave heating are
different from those of the conventional heating methods, the
mechanisms of the chemical reaction, nucleation, and growth of
inorganic nanostructures in liquid phase are also different using
different heating methods. Although a large volume of
experimental data on microwave-assisted syntheses has been
documented in the literature, the detailed mechanisms of the
chemical reaction, nucleation, and growth of inorganic
nanostructures in liquid phase under microwave irradiation
have still not been fully understood, and some important issues
such as the nonthermal effects or specific microwave effects
under microwave irradiation have not been clearly solved. The
existence of nonthermal effects or specific microwave effects
under microwave irradiation has been controversial and under
intense debate. Therefore, more carefully designed comparative
studies between the microwave heating and conventional
heating are necessary for further understanding of the
microwave heating mechanisms.
Although the comparative studies between the microwave
heating and conventional heating are essential for further
understanding of the microwave heating mechanisms, many
literature reports were based on inaccurate comparisons, which
could not reach unequivocal conclusions about microwave
effects, leading to some contradictions and controversies in this
research field. One of the fundamental difficulties facing all
comparative studies between the microwave heating and
conventional heating is the discrepancies between different
experiments in terms of the microwave field homogeneity (e.g.,
multimode or single mode microwave oven), size and geometry
of microwave cavity and reaction vessel, volume of reaction
system, stirring of recation system, microwave power, heating
rate, heating temperature, and heating time, etc. Unfortunately,
in many cases, the microwave-assisted syntheses were often
compared to the experimental data from those that were
performed under completely different conditions such as
different reaction temperatures and reaction times, and the
conclusions drawn from these comparisons are usually
inaccurate and speculative. Therefore, it is strongly recom-
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Chemical Reviews Review

mended that the comparative studies between the microwave Canada, from 1997 to 1998. He worked as an Alexander von
heating and conventional heating should be conducted under Humboldt Research Fellow at Fritz-Haber Institut der Max-Planck-
exactly identical experimental conditions. However, the Gesellschaft, Germany, from 1998 to 1999. He then worked as a
challenge is that the rapid and unique temperature profiles of Postdoctoral Fellow at the University of Utah and the University of
microwave heating are very difficult, if not impossible, to be Delaware, from 1999 to 2002. In 2002, he was selected by the Chinese
duplicated by the conventional heating. Therefore, the Academy of Sciences under the Program for Recruiting Overseas
comparisons of the microwave heating processes with conven- Outstanding Talents (Hundred Talents Program), and started to work
tional heating ones under the exactly same conditions are as a full Professor and a group leader at Shanghai Institute of Ceramics,
inherently challenging. CAS. He won “Excellence” in the Hundred Talents Program in 2005.
Some future research trends and directions are expected as He was selected under the Program of Shanghai Subject Chief
follows: (1) the in-depth understanding of the detailed Scientist in 2007. In 2009, he and his colleagues won the First Class
mechanisms of the chemical reaction, nucleation, and growth Prize of Natural Sciences of Shanghai (ranked No. 2). He has been
of inorganic nanostructures in liquid phase under microwave working in the research area of microwave-assisted preparation of
irradiation; (2) carefully designed comparative studies between nanostructured materials for many years. He has published more than
the microwave heating and conventional heating to clarify some 230 peer-reviewed journal papers, and has more than 20 granted
important issues such as the nonthermal effects or specific patents. He is currently an Editorial Board/Editorial Advisory Board
microwave effects under microwave irradiation, which have member of six journals. His current main research interests involve
been controversial and under intense debate; (3) theoretical
nanostructured biomaterials and microwave-assisted preparation of
and computer simulations of microwave effects and microwave
nanostructured materials.
heating mechanisms; (4) research on the microwave-assisted
precise control over the chemical composition, structure, size,
morphology, and self-assembly of nanostructures; (5) to
develop environmentally friendly microwave-assisted synthesis
methods at low cost and high efficiency; (6) investigation on
scaling up microwave-assisted large-scale production of
inorganic nanostructured materials, such as continuous flow
microwave synthesis; and (7) investigation on the relationship
of structure−property and applications of microwave-prepared
nanostructured materials. The realization of these targets will
greatly advance microwave chemistry and its wide practical
applications in rapid microwave-assisted controlled syntheses of
inorganic nanostructured materials in liquid phase, both at the
laboratory level and on the industrial scale.

AUTHOR INFORMATION
Feng Chen was born in 1981 in Anhui, China. He received his B.S. in
Corresponding Author Biology from Anhui Normal University in 2005, and received his M.S.
*Tel: +86-21-52412616. Fax: +86-21-52413122. E-mail: y.j. in Chemistry under the supervision of Prof. Xiu-Mei Mo from
zhu@mail.sic.ac.cn. Donghua University in 2008. He then joined the research group of
Notes Professor Ying-Jie Zhu at Shanghai Institute of Ceramics, Chinese
The authors declare no competing financial interest. Academy of Sciences. His current research interest focuses on the
microwave-assisted synthesis, properties, and applications of nano-
Biographies structured materials.

ACKNOWLEDGMENTS
The financial support from the National Natural Science
Foundation of China (51172260, 51121064), the National
Basic Research Program of China (973 Program, No.
2012CB933600), and the Science and Technology Commis-
sion of Shanghai (11nm0506600) is gratefully acknowledged.

ABBREVIATIONS
1-D one-dimensional
[BMIM][BF4] 1-n-butyl-3-methylimidazolium tetrafluorobo-
rate
BSA bovine serum albumin
Ying-Jie Zhu is a full Professor at Shanghai Institute of Ceramics, CTAB cetyltrimethylammonium bromide
Chinese Academy of Sciences (CAS). He received his Master degree DMF N,N-dimethylformamide
and Ph.D. at the University of Science and Technology of China EDTA ethylenediaminetetraacetic acid
(USTC) in 1992 and 1994, respectively. He worked as Assistant EG ethylene glycol
Professor and Associate Professor at USTC from 1994 to 1997. He HAP hydroxyapatite
then worked as a Visiting Professor at University of Western Ontario, HMTA hexamethylenetetramine
6540 dx.doi.org/10.1021/cr400366s | Chem. Rev. 2014, 114, 6462−6555
Chemical Reviews Review

P123 poly(ethylene glycol)-block-poly(propylene (33) Bogdal, D. Microwave-Assisted Organic Synthesis-One Hundred

glycol)-block-poly(ethylene glycol)
PEG poly(ethylene glycol)
PVP poly(vinylpyrrolidone)
SAED selected-area electron diffraction
SDS sodium dodecyl sulfate
SEM scanning electron microscopy
TEOS tetraethyl orthosilicate
TEM transmission electron microscopy
XRD X-ray powder diffraction
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